201243008 六、發明說明： 【發明所屬之技術領域】 本發明係關於適躲嘴騎刷方式的皮膜纽之乳液型 黏合劑、及含有其之喷墨用水性顏料墨水、液合劑 之製造方法。 【先前技術】 喷墨印表機的用途隨近年的高機能化而有多種分支用 途。例如，不僅作為個人用、事務用、業務用、記錄用、彩 色顯示用、彩色照片用，亦作為產業”墨印表機，且其用 途正進—步擴大。其中，關於產業用噴墨印表機，係特別要 求能因應高速印刷。_噴墨印表機所使㈣水性顏料墨 水，為達鮮雜、色澤清澈及顏色料等的提升，正朝顏料 粒子微細化演進。另—方面，為經由印表機裝置的改良而因 應高速化與高晝質化，係朝吐出液滴（墨水液滴）微小化演 進。此種&良對於喷墨用加卫紙，特別係相紙、寬幅用紙等， 可帶來優異的高畫質。然、而’尚無法對各種紙質均能適應列 印。特別係依據紙的種類’依此會產生列印物缺損的新問題。 再者，近年來，就產業用而言，多數係對由氯乙稀、聚婦 PET、及聚苯乙烯等所構成之各種薄膜基材施行印刷。 對該等賴基材亦必卿柄接性高的印刷皮膜(列印物）。 、為解決上述各種問題，已有將形成印刷皮膜的黏合劑添加 ;土 Jc中於是，便需要能因應各種紙質，並且對各種薄膜 101108433 3 201243008 均能形成密接性高之印刷皮骐，且喷墨印刷適性（高迷印刷 性、吐出安定性）良好的皮膜形成用黏合劑。另外，以下亦 將紙與薄膜合併記為「基材」。 但是，印表機的印頭處會有墨水呈現乾燥的情況。因此， 喷墨墨水便需要即便在印頭呈現乾燥及固著的情況，仍可藉 由洗淨液等輕易地予以溶解或分散而除去的再溶解性。 在此種背景下，近年已有開發出各種皮膜形成用黏合劑。 具體而言，已知將含有能成為通常的皮膜成分之丙烯酸系、 胺曱酸酯系、乙烯系等水溶性聚合物的溶液或乳液使用為黏 合劑。然而，因為水溶性聚合物係屬於溶解於水性顏料墨水 的水系介質中之成分，因而會有墨水黏度變高的問題。又， 已有在水雜聚合物中預先提高誠濃度，藉由彻驗中和 物施行中和而提升水溶性者。此種聚合物確實可使再溶解性 呈良好’但聚合物幾乎均溶解於水系介質中。因此，會有墨 水黏度更加提高賴向。又，墨水呈非牛頓性純會有無 法從印頭良好吐出的情況。且，因為聚合物中的縣較多， 因而會有卿成之皮膜的耐水性並不良好的情況。 相對於此’已有嘗試將藉由降低缓基的漢度使聚合物的溶 解性降低並粒子化而形成水分散體或乳液者（聚合物乳 液使用為黏合劑。此種黏合劑係可使墨水的黏度降低， 且聚合物中的絲濃度較低，因而所形成之皮膜的财水性呈 良好。且’因為聚合物本身屬於疏水性，因而所形成之皮膜 101108433 4 201243008 與基材間之密接性提升。然而，因為此種聚合物缺乏水溶 性’因而會有墨水的再溶解性不良的傾向。因此，必: 水溶性溶劑。 再者，當作黏合劑使用的聚合物乳液，已有提案藉由使用 以往公知的低分子界面活,_或反應性界面活_之乳化 聚合所獲㈣乳液；少量添加具錢基的單體並施行聚合 後，再施行中和而獲得的自行乳化型乳液（參照專利文獻 1〜3)。因為該等乳液中所含有的聚合物係屬於高分子量，因 而所形成之皮膜與基材間之密接性提升。然而，該等=液中 所含有的聚合物若乾燥㈣成皮膜，便難以溶解n 中，因而會有墨水的再分散性不良之傾向。 質 [先前技術文獻] [專利文獻] [專利文獻1]曰本專利特表2003·520279號公報 [專利文獻2]曰本專利特開2〇〇4_197〇9〇號公報 [專利文獻3]日本專利特開2〇〇5-179679號公報 【發明内容】 (發明所欲解決之問題） 本發明係有鑑於此種習知技術所存在的問題而完成，其課 題在於提供：能調製具有優異的吐出安定性，： 水性及對基材的密接性均優異之列印皮膜，且即便^口 (印頭）等乾燥仍可予以再溶解並輕易除去㈣墨用水性顏 101108433 5 201243008 料墨水之乳液型黏合劑、以及其製造方法。 再者，本發明的課題在於提供：具有優異的吐出安定性， 同時可形成耐水性及對基材的密接性均優異之列印皮膜，且 即便吐出口（印頭）等乾燥仍可予以再溶解並輕易除去的喷 墨用水性顏料墨水。 (解決問題之手段） 本發明者等人經深入鑽研，結果發現藉由將含有成為皮膜 高密接成分且實質上不溶於水的A聚合物嵌段、及高濃度 含有羧基且水溶解性高的B聚合物嵌段所構成的丙烯酸系 嵌段共聚物(A-B嵌段共聚物）之乳液型黏合劑，作為墨水的 皮臈形成用黏合劑，便可解決上述問題。 因此，上述課題係由以下所示之本發明而獲得解決。即， 根據本發明，係提供一種乳液型黏合劑，係含有構成成分之 90質量％以上為（甲基）丙烯酸酯系單體，且含有A聚合物嵌 B a-B , Α_Β嵌段共聚物的數量平均分子量為5,000〜1〇〇,〇00，且分 子量分佈（重*平均I子量/數量平均分子量）為 1.7以下；上 述。Α聚合物嵌段的酸值為〇〜3〇mgK〇H/g，且玻璃轉移點為 〇C以下’上述B聚合物嵌段的酸值為75〜25〇mgK〇H/g ; /述A-B敌段共聚物會被鹼物質所中和而在水系介質中自 仃礼化，形成數量平均粒徑3〇〜3〇〇nm的乳液粒子。 再者’根據本發明’係提供一種喷墨用水性顏料墨水，係 l〇U〇8433 201243008 含有顏料及皮膜形成用黏合劑者，其特徵為，上述皮膜形成 用黏合劑係上述乳液型黏合劑。 本發明中，較佳為上述顏料係從染料索引號碼(c.i.)顏料 藍-15 : 3 及 15 : 4 ; C.I.顏料紅-122 及 269 ; C.I.顏料紫-19 ; C.I.顏料黃-74、155、180 及 183 ; C.I.顏料綠-7、36 及 58 ; C.I.顏料橙-43 ; C.I.顏料黑-7 ;以及C.I.顏料白-6所構成群 組中選擇之至少一種，且數量平均一次粒徑未滿350nm;相 對於墨水總量（100質量％)，上述顏料的含有比例為4〜15質 量％，上述皮膜形成用黏合劑的含有比例為5〜20質量％。 再者，根據本發明，係提供一種乳液型黏合劑之製造方 法，係上述乳液型黏合劑的製造方法，其特徵為，係包括有： 至少將碘化合物使用為聚合起始化合物，使上述（甲基）丙烯 酸酯系單體進行活性自由基聚合，而合成上述A-B嵌段共 聚物的步驟。 本發明中，較佳為將從由鹵化磷、亞磷酸酯系化合物、及 次膦酸酯化合物構成的磷系化合物群組；由醯亞胺系化合物 構成的氮系化合物群組；由酚系化合物構成的氧系化合物群 組；以及由二苯基曱烷系化合物、及環戊二烯系化合物構成 的烴化合物群組所構成之化合物群組中選擇之至少一種化 合物使用為觸媒，而合成上述A-B嵌段共聚物。又，進行 上述活性自由基聚合時的聚合溫度較佳係30〜50°C。 本發明中，較佳為在水溶性有機溶劑中進行上述活性自由 101108433 7 201243008 基聚合後，添加驗物質進行中和，接著與水混合而使上述 A-B嵌段共聚物自行乳化。 (發明效果） 本發明的乳液型黏合劑中所含有的特定嵌段共聚物，係存 在於墨水中時不會溶解，能以粒子形式存在。因此，若使用 本發明的乳液型黏合劑，便可提供黏度低、吐出安定性優 異、能因應高速印刷的喷墨用水性顏料墨水。又，若使用本 發明的乳液型黏合劑，便可調製能形成具有耐水性、及對紙 與薄膜等基材呈優異密接性之列印皮膜的喷墨用水性顏料 墨水。再者，若使用本發明的乳液型黏合劑，便可調製即便 吐出口（印頭）等乾燥，仍可予以再溶解並輕易除去（具有再溶 解性）的喷墨用水性顏料墨水。 【實施方式】 1.乳液型黏合劑 以下，針對本發明的詳細内容，係舉用以實施本發明的形 態為例進行說明。本發明的乳液型黏合劑中所含有的聚合 物，係構成成分之90質量％以上為（曱基）丙烯酸酯系單體的 A-B嵌段共聚物。該A-B嵌段共聚物的數量平均分子量係 5,000〜100,000，且分子量分佈（重量平均分子量/數量平均分 子量）係1.7以下。另外，A-B嵌段共聚物係含有A聚合物 嵌段與B聚合物嵌段。A聚合物嵌段係酸值為 0〜30mgKOH/g，玻璃轉移點為00°C以下，且實質上不溶於 101108433 8 201243008 水的聚合物嵌段。又，B聚合物嵌段係酸值為 75〜250mgKOH/g，且實質上可溶於水的聚合物嵌段。 A-B嵌段共聚物係構成成分之90質量％以上、較佳係％ 質量％以上為（曱基）丙嫦醋系單體。（曱基）丙烯酸醋系單 體係可使用以往公知者’並無特別限定。作為（甲基）丙烯酸 _系單體的具體例’係列K甲基稀酸曱醋、（曱基)丙 稀酸正丁 i旨、（曱基）丙烯酸環己S旨等脂肪族或脂環族醇的（甲 基)丙烯咖旨；（甲基)丙稀酸节醋、（曱基)丙稀酸笨氧基乙醋 等含有芳香環的（曱基）丙烯咖旨；（甲基）丙稀酸曱氧基乙 醋、（曱基）丙稀酸乙氧基乙氧基乙略、（甲基）丙騎聚㈣ 以上）乙二醇等二醇的（甲基）丙稀酸賴；（曱基)丙稀酸純乙 醋、（甲基)丙烯酸旨等含羥基的（曱基)㈣酸醋；（甲 基)丙烯酸二甲基胺基乙醋、（甲基)两締酸二乙基胺基乙醋等 含胺基的（甲基）丙婦酸醋；（甲基）丙缔酸環氣丙酿、（甲基） 丙烯酸四氫細旨、（曱基)丙稀酸氧雜環丁酉旨等氧環料甲基） 丙烯酸Κ甲基)丙稀酸U，2,2_四氣乙酉旨等含氣:子的(土甲 基)丙烯酸醋；末端為（甲基)丙婦酸酉旨基的笨乙稀巨單體、聚 石夕氧巨單體、^己内紅單體；甲基丙_ 2_[3调_苯 并三唾·2·基Μ·經苯基]乙酿、（甲基）丙烯酸3,3,5,5•四甲基 哌啶等使耐光性提升的（甲基）丙烯酸酯等等。 在構成成分之90質量％以上為（甲基）丙稀酸酿系單體之 前提下，亦可將「其他的加絲合性單體」與（？基)丙_ 9 101108433 201243008 料單體—併使用。作為「其他的加成聚合性單體」的具體 《！係可列舉.苯乙婦、乙晞基甲苯、（甲基)丙烯醯胺系單 體（曱基)丙稀腈系單體、燒酸乙婦醋系單體等。 A B 共聚物的酸值係在特定數值範圍内。因此，作為 構成A B紐絲物的單體，㈣係使祕有酸基的（曱基) 丙稀酉夂系化合物。該酸基係可列舉如：叛基、確酸基、破酸 基等。其中’就從耐水性與取得容易度的觀點，較佳係使用 具有叛基的（甲基）丙稀酸系化合物。作為具錢基的（曱基) 丙稀酸系化合物，係可列舉如：（甲基)丙烯酸、丙烯酸二聚 體、伊康酸、順丁烯二酸、敵酸、巴豆酸、献酸或順丁稀二 酉欠等一元酸與（曱基）丙烯酸2_羥乙酯等含有羥基的單體進 行半酯化而獲得的單體等。其中，就從聚合性的觀點，特佳 為（曱基）丙稀酸。 其次，針對構成A-B嵌段共聚物的A聚合物嵌段與B聚 合物嵌段分別進行說明。另外，A_B嵌段共聚物係2個嵌段 進行鍵結而成的嵌段共聚物，為求便利，係將其中一聚合物 嵌段稱「A聚合物嵌段」，將另一者稱「B聚合物嵌段」。 (A聚合物嵌段） A聚合物嵌段係適當選擇上述各種單體進行聚合而成的 聚合物嵌段。A聚合物嵌段的酸值係〇〜3〇mgK〇H/g、較佳 係0〜20mgKOH/g。因為酸值在上述範圍内，因而a聚合物 嵌段係實質上不溶於水。因此，當使含有A聚合物嵌段的 101108433 10 rs 201243008 A_B錢絲物分散於水系介質巾並進行乳液化時，可認為 A聚^物嵌段係將成為形成粒子的部分1外，藉由在上述 酸值粑圍内，使A聚合物嵌段中含有少量酸基，便可調整 v、基材間之也、接性、及乳液粒子的粒徑。 A聚合物喪段的玻璃轉移點（以下亦記為、」）係卿以 :、較佳係5〜5〇。〇因為Tg在上述範圍内，因而乳液型黏 a劑的造膜性提升。更佳係Tg為室溫(25。〇以下，若U為 6〇C以下，利用在墨水中添加造_劑等便可提高造膜性。 A聚合物嵌段的Tg係可在A聚合物嵌段進行聚合後，利 用熱分析進行測定，亦可簡易地求取。例如，在由X成分的 单體進行共聚合*成之聚合物(絲合體)的情況，若將各個 單體的質量(g)假設為「Wi、W2、· · .Wx」，將各個單體的 同元聚合物之Tg(°C)假設為「丁丨、τ2、· · · T 口主 Αχ」崎，便可 從下式（1)計算出該共聚合體的Tg(T(°c)): l/T=Wl/(Tl+273)+W2/(T2+273)+ · · · Wx/(Tx+273) · · ·⑴ 同元聚合物的Tg值亦可使用「高分子手冊第4版」所 記載的數值，此外，亦可使用各種文獻的數值。另外本發 明係使用「高分子手冊第4版」所記載的數值。 藉由存在A聚合物嵌段，A-B嵌段共聚物便會粒子化， 且實質上不溶於水。故，含有A-B嵌段共聚物的乳液型黏 合劑之黏度會降低。因此，即便將該乳液型黏合劑添加於黑 水中’墨水的黏度仍不太會上升，墨水的吐出安定性良好 101108433 11 201243008 又，因為A-B嵌段共聚物係實質上不溶於水，因而若使用 採用含有該A-B嵌段共聚物之乳液型黏合劑的墨水，便可 形成對基材呈高密接性的列印皮膜。 (B聚合物嵌段） B聚合物嵌段的酸值係75〜250mgKOH/g、較佳係 100〜200mgKOH/g。因為酸值在上述範圍内，因而B聚合物 嵌段便實質上可溶於水。若B聚合物嵌段的酸值未滿 75mgKOH/g ’則再溶解性會降低。另一方面，若b聚合物 嵌段的酸值超過250mgKOH/g，便會有所形成之列印皮膜的 耐水性差之情況。另外，藉由將B聚合物嵌段中的酸基利 用氨、胺、氫氧化鈉等驗物質施行中和，B聚合物篏段便成 為可溶於水中的聚合物嵌段。當A聚合物嵌段施行粒子化 之際，B聚合物嵌段會溶解於水中。藉此，嵌段共聚物 的粒徑便受控制，俾可使A-B嵌段共聚物的粒子能安定地 存在（分散)於水系介質中。又，使用該Α·Β嵌段共聚物所調 製的噴墨用水性顏料墨水，即便印頭乾燥，仍可利用Β聚 合物嵌段的高水溶性而呈現出優異的再溶解性。 Β聚合物嵌段中的酸基係在墨水中被中和。因此，Β聚合 物嵌&可謂屬於對水呈溶解性的嵌段。故，使用含有異有Β 聚^物嵌段的A-Β嵌段共聚物的乳液型黏合劑之墨水，即 便土出d(印頭）等處乾燥，仍可利用水等洗淨液輕易地予以 溶解，呈現優異的再分散性。 101108433 12 201243008 (A-B嵌段共聚物） A-B嵌段共聚物的數量平均分子量（以下亦記為「Mn」） 係5,000〜100,000、較佳係8,000〜5〇,〇〇〇。另外，Μη在無特 別聲明的前提下’係指利用凝膠滲透色層分析儀（以下亦記 為「GPC」）所測定的聚苯乙烯換算值。Α_Β嵌段共聚物的 Μη係Α聚合物嵌段的Μη、與Β聚合物嵌段的Mni合計。 所以’在A-B欲段共聚物的Μη為上述數值範圍内之前提 下’Α聚合物嵌段與Β聚合物嵌段的各自Μη&無特別限定。 若Α-Β嵌段共聚物的Μη未滿5,〇〇〇,則因為分子量過小， 因而使用喷墨用水性顏料墨水所形成之列印皮膜的密接性 等物性難以獲得提升。另一方面，若α_β嵌段共聚物的Μη 過大，則無法對喷墨用水性顏料墨水賦予再溶解性。 以Α-Β嵌段共聚物的重量平均分子量（以下亦記為「Mw」) 對數1平均分子量(Μη)的比值(Mw/Mn)表示的分子量分佈 (以下亦記為「PDI」）係1.7以下、較佳係！ 6以下。 A B肷^又共聚物中所含A聚合物嵌段與b聚合物飯段的 質量比，較佳係A/B=20/80〜95/5、更佳係a/B=30/70〜90/10。 若A聚合物嵌段與B聚合物嵌段的質量比在上述範圍内， 則構成A-B嵌段共聚物的水不溶性部分(A聚合物嵌段）、與 水溶性部分(B聚合物欲段）間之均衡便呈良好。 A-B嵌段共聚物係例如在其中一聚合物嵌段進行聚合 後，添加構成另一聚合物嵌段的單體成分，再進一步進行聚 101108433 13 201243008 合便可合成。此處，若剛開始進行聚合的其中一聚合物嵌段 之PDI較大，則後面進行聚合的另一聚合物嵌段之PDI便 會變得更大。若所獲得A-B嵌段共聚物的PDI過大，則會 有A-B嵌段共聚物的乳液化趨於困難，且喷墨用水性顏料 墨水的再溶解性不足之傾向。所以，藉由預先將剛開始進行 聚合的其中一聚合物嵌段之PDI縮小某程度’俾使最終所 獲得A-B嵌段共聚物的pdi在1.7以下，便可使A-B嵌段 共聚物良好地乳液化，並可提升喷墨用水性顏料墨水的再溶 解性。 (乳液型黏合劑） 本發明的乳液型黏合劑係A-B嵌段共聚物利用鹼物質進 行中和’並在水系介質中自行乳化而形成乳液粒子者。又， 所形成乳液粒子的數量平均粒徑係30〜300nm、較佳係 50〜200nm。若乳液粒子的數量平均粒徑未滿3〇nm，便會有 乳液粒子過細，導致墨水的黏度上升之情況。另一方面，若 乳液粒子的數量平均粒徑超過300nm，則會有喷墨印頭容易 遭阻塞’導致吐出趨於困難的情況。 舉例而言，A-B嵌段共聚物係在聚合後直接、或暫時先取 出後，在水系介質中添加鹼物質，使A_B嵌段共聚物的酸 基被中和。因為A聚合物嵌段係屬於實質上不溶於水的嵌 段，因而對A-B嵌段共聚物的粒子化具貢獻。另一方面， 因為B聚合物嵌段係屬於實質上可溶於水的嵌段，因而使 101108433 201243008 A-B嵌段共聚物自行乳化㈣成安定的乳液 液粒子的數量平均粒麵可朗以往公 夕，礼 發明的數量平均粒_%_ ♦如測疋。本 裝置(例如商品名「，咖」、 公=的粒徑測定 為了，和…段共聚物的酸基所使用測定。 特別限定，可列舉：氨.二7 ^ <鹼物質’並無 胺等有機胺，·氫氧化納Ί $女、—甲基胺基乙醇、三乙醇 再者，上氧_秘麵魏化物。 再者上述水系,丨質係可單獨為水，亦可 機溶劑的混合溶劑。作為水溶性有機溶劑的=例水=有 舉：乙醇、異丙醇等水可溶性低級脂肪族醇^酮等 溶:r:r:_可一⑽=醇 一 I 甲科水可溶性_溶劑；丙二醇 二醇及其早㈣等水可溶性二醇系溶劑；Ν· 水溶性醯㈣溶劑；甘油、仏己二料水可雜多凡= 劑等等。另外，該等水溶性有機溶劑係可單獨使用一種、: 組合使用二種以上。另休，6“、，m ^ 斤併用的水溶性有機溶劑的量係 為任意。 ' 本發明的乳液型點合劑較佳係在水溶性有機溶劑中將 A-B敌段絲物進行聚合之後，⑴添祕㈣的水溶液而中 和A-B嵌段共聚物的酸基俾使自行乳化而進行調製，或者⑼ 添加驗物質而仲Α·Β嵌段絲物㈣基之後，再添加水 1 俾使自行乳化而進行調製。藉由依此調製乳液餘合劑，便 101108433 201243008 可在不致發生析出與增黏的情況下，達成微粒子化。 2.喷墨用水性顏料墨水 其次，針對本發明的喷墨用水性顏料墨水的詳細内容進行 說明。本發明的噴墨用水性顏料墨水係含有顏料及皮膜形成 用黏合劑。而，該皮膜形成用黏合劑係前述乳液型黏合劑。 藉由將前述乳液型黏合劑使用為皮膜形成用黏合劑，便可成 為能形成具有高速印刷性及優異吐出安定性，且耐水性及對 基材的密接性均優異之列印皮膜，且即便吐出口（印頭）等乾 燥仍可予以再溶解並輕易除去的噴墨用水性顏料分散墨 水。另外’本發明的喷墨用水性顏料墨水中所含有之乳液型 黏合劑的比例，係相對於墨水總量（100質量％)，依固形份 濃度計，較佳為5〜20質量％、更佳為7.5〜15質量％。 (顏料） 顏料係可使用以往所使用之有機顏料或無機顏料之單獨 一種、或組合使用二種以上。作為顏料的具體例，係可列舉· 碳黑顏料、喹吖酮系顏料、酞青系顏料、笨并咪唑綱系顏料 異吲哚啉酮系顏料、偶氮系顏料、氧化鈦顏料等。 其中’顏料較佳係從喷墨墨水所使用顏料的染料索引號石馬 (C.I.)顏料藍-15 : 3 及 15 : 4 ; C.I·顏料紅_122 及 269 ; q 顏料紫·19 ; C.I.顏料黃-74、155、180及183 ; CI，顏料綠_7、 36及58 ; C.I.顏料橙-43 ; C.I.顏料黑-7 ;以及cj顏料白6 所構成群組中選擇之至少一種。 101108433 201243008 再者’顏料的數量平均一次粒徑較佳係未滿350nm，有機 顏料較佳係為150nm以下。特別係當顏料係使用C.I.顏料藍 久 15 · 4 ; C.I.顏料紅-122 及 269 ; C.I·顏料紫_19 ; C.1.顏料黃-74、155、180 及 183 ; C.I.顏料綠-7、36 及 58 ; c.i.顏料橙_43;以及c丄顏料黑_7的情況，該等顏料的數量 平均一次极徑較佳係150nm以下。 再者’ t顏料係使用CX顏料白·6的情況，C.I.顏料白-6 的數量平 习一次粒徑較佳係3〇〇nm以下。特別係若考慮印 頭阻塞、所形成影像的鮮銳性，則數量平均一次粒徑越小越 佳。 顏料係可為表面經導入官能基的自分散性顏料，亦可為經 利用偶合#卜活性劑等表面歧劑賴脂等對其表面施行處 I或、轉囊化等處理的顏料。另外，喷墨用水性顏料墨水 中所3有之顏料的比例’係相對於墨水總量(1GG質量％)， 較佳為2〜15質晉〇/ s 貝里/〇、更佳為4〜10質量％。 (顏料分散劑） 墨用水性顏料墨水中，較佳係含有顏料分散劑。特別係 顏料較佳係未使用自分散性顏料，因為當使用未具有自分散 =的曰通顏料(無機顏料、有機顏料)時，可使該等顏料依適 田狀匕、刀政’故屬較佳。顏料分散劑係可使用以往公知者， 並無特別限&。作為顏料分散劑的具體例，係可列舉：丙烯 夂系U笨乙烯'纟聚合物等無規聚合物、欲段共聚物型 101108433 17 201243008 分散劑、接枝聚合物型分散劑、星型聚合物型分散劑 枝型分散劑等。另外，嘴墨用水性顏料墨水中所含有之^ 分散劑的比例，係相對於黑>μ 又顋料 丁於墨水總量（100質量％)， 0.5〜15質量％、更佳為2〜1〇質量％。 平乂佳為 (其他成分） 本發明的喷墨用水性 及顏料分散劑以外的「 介質、各種添加劑等。 顏料墨水中’視需要尚可含有除顏料 其他成分」。「其他成分」係'可例示如 "質係可列舉.水、則述水溶性有機溶劑。作為水溶性 機溶劑的具體例’係可列舉：二乙二醇單獨、三乙二 丁醚、甘油、丙二醇、1 2· ρ — ，G —醇、2-°比。各σ定酮、甲基-2- 卜各咬酮等。藉由使用該等水溶性有機溶劑，便可更有效地 防止印頭的乾燥。另外’較佳係使_等水溶性有機溶劑-種以上’較佳亦可與水併用。嘴墨用水性㈣墨水中所含有 。之水溶‘H有機㈣的比例，係相對於墨水總量⑽質量 %) ’較佳為1〜40質量。/0、更佳為5〜2〇質量％。 〜作為各種添加劑的具體例，係可列舉：界面活性劑、顏料 物木料、均塗劑、消泡劑、紫外線吸收劑等。該等添 加劑的含有比例只要係在不致損及本發明效果的範圍内，其 餘並無特別限定。 3.乳液型黏合劑之製造方法 其次，針對乳液型黏合劑之製造方法進行說明。本發明的 101108433 201243008 乳液型黏合劑之製造方法，係包括有：至少將碘化合物使用 為聚合起始化合物’使（曱基）丙烯酸酯系單體進行活性自由 基聚合’而合成A-B嵌段共聚物的步驟。以下，針對其烊 細内容進行說明。 (A-B嵌段共聚物之合成步驟） A-B嵌段共聚物亦可利用習知的活性自由基聚人方法進 行合成。但，本發明中，A-B嵌段共聚物係由前述（甲基）丙 烯酸酯系單體進行活性自由基聚合而合成。又a 自施行活性 自由基聚合之際，碘化合物係使用為聚合起始化入物— 碘化合物使用為聚合起始化合物，利用熱或光所產 由基便會與單體產生反應，而生成聚合物太 、碘自 7不鳊自由基。因為 逐次產生的碘自由基會與聚合物末端自由 田基相鍵結而安定 化，故可防止發生終止反應。因為藉由此難複反應而進行 活性自由基聚合，所以可輕易地控制所獲得& 物的分子量與構造。 ^ 碘化合物係在屬於能利用熱或光的作用而產 之前提下，其餘並無特別限定。作為碰彳八 〃 G 5物的具體例，係 可列舉：2射苯基乙貌、…苯基乙貌等燒基硬化物； 2-氰基-2碘丙烷、2-氰基·2_碘丁烷、 乱暴-1-碘環己烷、2_ 氰基-2-碰戊腈等含氰基之蛾化物等等。 可直接使用市售物的礙化合物，亦可使用依照以往公知方 法所合成的视合物，化合物係例如藉岐偶氮雙異丁猜 101108433 19 201243008 等偶氣化合物、與峨進行反應便可獲得。又，亦可使用具有 /臭氯專除硬以外之鹵原子的有機齒化物，以及四級銨峨化 物、埃化鈉等;^化物鹽，使其在反應系統中發生鹵交換反應 而產生峨化合物。 再者活丨生自由基聚合時，較佳係使用能從蛾化合物中脫 離出硤原子而生成碟自由基的觸媒。作為此種觸媒，係可列 舉：鹵化麟、亞磷酸醋系化合物、次膦酸醋化合物等礎系化 合物，醯亞胺系化合物等氮系化合物·屬系化合物等氧系化 合物；二苯基曱院系化合物、環戊二婦系化合物等含活性碳 原子的烴化合物。另外，該等觸媒係可單獨使用一種、 合使用二種以上。 ~ 作為鱗系化合物的具體例，係可列舉：三破化碟、亞鱗酸 二乙醋、亞填酸二丁醋、乙氧基苯基次膦酸酿、苯基苯氧基 -人膦酸g旨等。作為氮系化合物的具體例，係可列舉：號轴酿 亞胺、2,2-二曱基琥拍醯亞胺、順丁稀二醢亞胺、駄酿亞胺、 N-碘琥珀醯亞胺、乙内醯脲等。作為氧系化合物的具體例， 係可列舉：酴、氫酿、甲氧基氫醒、第三丁細、兒茶紛、 二第三丁基經甲苯等。作為烴化合物的具體例，係可列舉： 環己二稀、三苯基曱院等。觸媒的使用量（莫耳數)係未滿後 述聚合起始劑的使用量（莫耳數）<3若觸媒的使用量過多，便 會有難以進行聚合的情況。 進行活性自由基聚合時的溫度，較佳係設為3〇〜咐。特 101108433 20 201243008 別係當使用曱基丙烯酸作為具有酸基的（曱基）丙稀酸系化 合物之情況’較佳係將進行活性自由基聚合時的溫度設為上 述溫度範ϋ内。若溫度過高，則聚合末端_自由基會因甲 土丙浠s夂而谷易分解，導致所形成聚合物末端不安定，會有 活性自由基聚合難以進行的情況。 ^進订活n自由基聚合時，為使較容易產生峨自由基，較佳 係添加聚合起始劑。該聚合起始劑係可使用偶氮系起始劑、 過氧化㈣起始财以往公知化合物。但，聚合起始劑較佳 係在上述聚合溫度能充分產生硬自由基的化合物。具體而 吕，係可列舉：2,2，_偶氮雙⑷曱氧基-2,4-二曱基戊腈）等偶 1系起始#卜聚合起始義使用量較佳躲為進行聚合 體之〇.001〜ο.1莫耳倍、更佳係設為〇.〇〇2〜〇.〇5莫耳倍。若 聚合起始劑的使用量過少，會有活性自由基聚合無法充分進 订的隋况°另"~方面’絲合起始劑的使用量過多，則會有 並非進行雜自纟絲合，岐鋪· it㈣自由絲合作為 副反應之可能性。 活性自由基聚合亦可為未使用有機溶劑的塊狀聚合，但較 佳係使用A劑的溶液聚合。溶劑較佳係可溶_化合物、觸 媒、單體及聚合起始_溶劑。其中，若考慮使顏料分散， 較佳係水溶性有機溶劑。 進行溶液聚合之際，聚合賴_份濃度(單體濃度)並無 特別限^ ’較佳係設為5~8G f量％、更佳係設為20〜的質 101108433 21 201243008 量％。若©形份濃度未滿5質量％，則單體濃度過低，會有 聚合未完全的可能性。另一方面’若固形份濃度超過8〇質 量％ ’則實質上成為塊狀聚合，導致聚合_度變為過高。 因此，會有攪拌趨於困難、且聚合產率降低的傾向。 活性自由基聚合較佳係執行至單體消失為止。具體而言， 聚合時間較佳係設為0.5〜48小時’實質上更佳係設為… 小時。又’聚合環境並無特別限定，可為在通常範圍内存在 氧的環境，亦可為氮氣流環境。又，聚合時所使用的材料(單 體等），係可使驗_、活性碳處理、或氧化减理等而 去除雜質者’亦可直接使料售物。又，亦可在㈣下施行 聚合，亦可在玻璃等透明容器中施行聚合。 其次’針對聚合的順序進行說明。A_B嵌段共聚物的聚合 順序較佳係(1)使疏水性單體進行聚合而形成A聚合物嵌段 之後’（ii)添加構成B聚合物嵌段的單體，再進一步施行聚 合。若使構成B聚合物嵌段的單體先進行聚合便會有聚 合未完全，導致？基丙烯g㈣具該基的單誠存於反應系 統内的情況。此種情況，具有酸基的單體容易被導入於A 聚合物嵌段’會有損及所形成A聚合物嵌段之疏水性（導致 酸值超過既定範圍）的情況。相對於此，若使構成A聚合物 嵌段的單體先進行聚合，即便聚合未完全而在反應系統内殘 存單體的情況Ί依所獲得Α·Β嵌段共聚物的構成成分 之90質量％以上成為（甲基)丙稀酸g旨系單體之方式導入Β 101108433 22 201243008 聚合物嵌段，便可輕易地獲得A-B嵌段共聚物。 藉由調整聚合起始化合物(碘化合物）的使用量，便可控制 所獲得Α·Β嵌段共聚物的分子量。具體而言，相對於聚合 起始化合物的料數，藉㈣當地狀單體的莫耳數，便可 獲得任意分子量的Α_Β纽共㈣。例如，❹丨莫耳之 聚合起始化合物’且使用遍莫耳之分子量的單體並進 =聚合時，便可獲得具有「lx⑽x5GG=5q，_」之理論分子 里的A B 共聚物。即，A_B嵌段共聚物的理論分子量 係可依下式(2)計算出。另外，上述「分子量」係數量平均 刀子置(]\411)與重1平均分子量(Mw)均涵蓋在内的概念。 「A-B嵌段絲物的理論分子量」=「聚合起始化合物ι 莫耳」X「單體分子量」x「單體的莫耳數/聚合起始化合物 的莫耳數」· · ·（2) 另外上述4性自由基聚合時因為會有衍生二分子停止 ^不=化的副反應之情況，因而會有無法獲得具有上述理論 分子量的Α·Β嵌段共聚物之情況。—嵌段共聚物較佳係 在未產生該等4反應的情況下所獲得者。但，亦可為因偶合 而使獲付之Α·Β嵌段共聚物的分子量多少有變大，亦可為 聚合反應錢中停止錢獲得之α·β纽共㈣的分子量 多少有變小。又，聚合率亦可非為100%。又，亦可在聚合 暫時結束彳i添加聚合絲劑或觸媒，；肖耗赫的單體，俾 使聚合結束。β卩’只要能生成Α·Β嵌段共聚物便可。 101108433 23 201243008 所獲得a-B嵌段共聚物係可維持鍵結著源自當作聚合起 始化合物使用的碘化合物之碘原子的狀態，但較佳係使碘原 子脫離。使埃肩子從A-JB嵌段共聚物脫離的方法，係在為 以往公知方法之前提下，其餘並無特別限定。具體而言，: 要對Α·Β嵌段絲物騎加熱、糾賴錢施行處°讀 可。又，亦可利用硫代硫酸納等對Α-Β嵌段共聚物施行處 理。所脫_韻、可_活性碳、氧化料魏附劑施行處 理而除去。 若利用驗物質巾和賴狀Α_Β嵌段共㈣，使其在水 系介質中進行自行乳化，便可獲得含有數量平均粒徑為 30〜30〇nm之乳液粒子的乳液型黏合劑。另外，本發明中， 較佳係⑴在水溶性有機溶劑中進行上述活性自由基聚合⑼ 然後:在反應系統中添加驗物質而進行中和，（iii)接著，與 水混。而使A_B嵌段共聚物自行乳化。藉此，便可輕易地 調整所形魏I料的數量平均粒徑。 4’喷墨用水性顏料墨水之製造方法 其-人’針對喷墨用水性顏料墨水之製造方法進行說明。喷 1用Kf生顏料墨水係藉由例如⑴使顏料分散於水系介質中 顏料分散體，⑼將所獲得誠分散體與乳液型點合 J見〇 (111)視需要添加添加劑等，便可進行製造。 顏料分散體係可利用以往公知的方法進行調製。例如，只 要將顏料_分散劑及水丨介質予以混合，視需要添加活 101108433 ΓΘ 24 201243008 性劑等添加劑，便可獲得顏料分散體。當顏料係使用有機顏 料的情況，顏料分散體中所含之有機顏料的比例，相對於墨 水總量，較佳係設為10〜30質量％。又，當顏料係使用無機 顏料的情況，顏料分散體中所含之無機顏料的比例，相對於 墨水總量，較佳係設為40〜70質量％。 顏料分散體中所含之顏料分散劑的比例，相對於顏料1〇〇 質量份，較佳係設為5〜30質量份。另外’當顏料係使用自 分散性顏料的情況，亦可未使用顏料分散劑。在將各成分混 合而使顏料分散時，可使用例如：捏合機、雙輥機 '三輥機、 MIRACLE KCK(淺田鋼鐵公司製’商品名）之類的混練機； 超音波分散機；微射流均質機(Mizuho公司製，商品名）、微 粒機（吉田機械興業公司製，商品名）、Star Burst (Sugin〇 Machine公司製，商品名）、G_smasher (瑞顧斯公司製商 品名）等高壓均質機。又，亦可使用球磨機、砂磨機、臥式 研磨介質分散機、膠體磨碾機等利用磨珠介質者。 若考慮墨水的發色性、列印品質、及墨水中的顏料沉降 等’當使用有機顏料的情況’顏料分散體中的有機顏料之數 量平均一次粒徑較佳係i5Qnm以下。又當使用無機_ 的情況，麵分散體中的無機肺之數量平均-次粒徑較佳 係300mn以下。另外’為能獲得依所需粒度分佈分散顏料 的顏料分散體，可採用例如：_小分散機的粉碎介質尺 寸、⑼增大粉碎介質的填充率、⑽延長處理時間、㈣減 101108433 •·Λ 25 201243008 緩吐出速度、（V)經粉碎後再利用過濾器、離心分離機等施 行分級等等手法。又，亦可組合該等手法。又，亦可使用經 鹽磨法等以往公知之方法預先磨細的顏料。各成分經混合及 分散後，較佳係利用離心分離機或過濾器去除粗大粒子。 若將所獲得之顏料分散體、水系介質、及屬於皮膜形成用 黏合劑的乳液型黏合劑、以及視需要使用的添加劑，依照常 法進行混合，便可獲得本發明的喷墨用水性顏料墨水。 從將依喷墨施行列印的點陣徑擴展為最佳寬度之觀點而 吕’喷墨用水性顏料墨水的表面張力較佳係20〜40rnN/rne 為使喷墨用水性顏料墨水的表面張力在上述數值範圍内，較 佳係在噴墨用水性顏料墨水中添加界面活性劑。界面活性劑 係可使用以往公知者。若界面活性劑的添加量過多，會有損 及顏料分散安定性的情況。因此，噴墨用水性顏料墨水中所 含有之界面活性劑的比例，較佳係設為001〜5質量％、更 佳係設為0.1〜2質量％。 本發明的喷墨用水性顏料墨水的黏度並無特別限定，當使 用有機顏料的情況，較佳係2〜1〇mPa · s。又，當使用無機 顏料的情況，較佳係5〜30mPa· s。 [實施例] 其次’列舉實施例與比較例以針對本發明進行更具體說 明。惟，本發明並不因該等例子而受任何限定。另外，文中 「份」與「％」均係依質量基準。 !〇Π〇8433 26 201243008 (1)乳液型黏合劑之調製 (實施例1 :乳液型黏合劑（1)之調製） 在具備有授拌機、回流冷凝器、溫度計及氮導入管的 . 分離式燒瓶中，裝填入：二乙二醇二曱醚（以下記為「DMDG」) - I31.7份、碘1.0份、2,2’-偶氮雙(4-曱氧基-2,4-二甲基戊腈） (以下記為「V-70」）4.9份、曱基丙烯酸苄酯（以下記為 「BzMA」）44份、甲基丙烯酸厶羥乙酯（以下記為「Hema」） 13份、及Ν·峨琥拍酿亞胺0.11份。攪拌並加溫至4(rc，進 行聚合。3小時後，碘的褐色消失。從此時起，碘與v_7〇 進行反應，可確認到在反應系统内有生成碘化合物（聚合起 始化合物）。將溫度保持一定，再進行4小時聚合後，經自 然冷卻，便獲得A聚合物嵌段的溶液。 對溶液其中一部分進行採樣，測定固形份濃度，結果為 27.5%。又’從所測定之固形份濃度計算出的聚合率係約 85%。又，經利用GPC分析A聚合物嵌段，結果施為7,獅、 PDI為1·31。所獲得之A聚合物嵌段的組成係 .BzMA/HEMA= 77/23，利用理論計算所計算出的丁笆係 . 54.2°C，酸值係OmgKOH/g。將所採樣的溶液其中—部分添 加於水中’結果會有樹脂析出。藉此可確認到所獲得之A 聚合物嵌段係屬於實質上不溶於水的聚合物。 在所獲得之A聚合物嵌段的溶液中，添加甲基丙稀酸甲 酯（以下記為「MMA」）52.8份、甲基丙烯酸（以下記為「MAA」) 101108433 27 201243008 12.9份、及ν-70 0.45份的混合物，進行4·5小時的聚合， 形成Β聚合物嵌段，而獲得Α-Β嵌段共聚物的溶液。聚合 率係約100%。在Β聚合物嵌段的構造中，含有源自屬於殘 留單體之BzMA與ΗΕΜΑ的構成單位。從產率所換算的Β . 聚合物嵌段之組成係ΜΜΑ/ΜΑΑ/殘留單體与71/17/12。又， · 從ΜΑΑ的含有量所計算出之Β聚合物嵌段的酸值係 110mgKOH/g。 所獲得之A七嵌段共聚物的Mn係14,〇〇〇、PDI係1.45。 在將所採樣的A_B嵌段共聚物〇.5份溶解於曱苯/乙醇 (體積比）5〇份中而獲得的試料中’添加當作指示劑的酚201243008 VI. [Technical Field] The present invention relates to an emulsion type adhesive for a film which is suitable for a smear and a method for producing an inkjet water-based pigment ink and a liquid hydrating agent containing the same. [Prior Art] The use of the ink jet printer has many branches and uses depending on the high performance in recent years. For example, it is used not only for personal use, business use, business use, recording, color display, color photographs, but also as an industrial ink printer, and its use is expanding. The watch machine is specially required to be able to print at high speed. _ Inkjet printers make (4) water-based pigment inks, which are improved in terms of fresh, bright color and color materials, and are gradually evolving toward pigment particles. In order to improve speed and high quality by the improvement of the printer device, the droplets (ink droplets) are gradually evolved toward the discharge. This kind of paper is used for inkjet paper, especially photographic paper. Wide-format paper, etc., can bring excellent high image quality. However, 'there is no way to adapt to printing on all kinds of papers. In particular, depending on the type of paper', new problems of print defects will occur. In recent years, in the industrial use, most of the film substrates are printed on various film substrates composed of vinyl chloride, poly-PET, and polystyrene. Film (printed matter). In view of the above various problems, a binder for forming a printing film has been added; in the case of soil Jc, it is necessary to be able to cope with various papers, and it is possible to form a printing skin with high adhesion to various films 101108433 3 201243008, and inkjet printing. Adhesives for film formation which are excellent in suitability (high printability and discharge stability) are also referred to as "substrate" in the following. However, there is a tendency for the ink to dry out at the print head of the printer. Therefore, the inkjet ink requires re-solubility which can be easily dissolved or dispersed by a cleaning liquid or the like even when the printing head is dried and fixed. Under such circumstances, various binders for film formation have been developed in recent years. Specifically, it is known to use a solution or emulsion containing a water-soluble polymer such as an acrylic, an amine phthalate or a vinyl which can be a usual film component as a binder. However, since the water-soluble polymer is a component dissolved in an aqueous medium of the aqueous pigment ink, there is a problem that the viscosity of the ink becomes high. Further, it has been previously possible to increase the concentration in the water-based polymer, and to improve the water solubility by performing neutralization of the neutralized substance. Such a polymer does provide good resolubility' but the polymer is almost uniformly soluble in the aqueous medium. Therefore, there is a tendency for the viscosity of the ink to increase. Also, if the ink is non-Newtonian, there will be no way to spit out from the print head. Further, since there are many counties in the polymer, the water resistance of the film of the crystal is not good. In contrast, it has been attempted to reduce the solubility of the polymer by particle reduction to form an aqueous dispersion or emulsion (the polymer emulsion is used as a binder. Such a binder can be used). The viscosity of the ink is lowered, and the concentration of the filament in the polymer is low, so that the formed film has a good water solubility. And because the polymer itself is hydrophobic, the formed film 101108433 4 201243008 is in close contact with the substrate. However, since such a polymer lacks water solubility, there is a tendency for the ink to have poor resolubility. Therefore, it must be: a water-soluble solvent. Further, a polymer emulsion used as a binder has been proposed. By using a conventionally known low molecular interface activity, _ or a reactive interface to obtain an emulsion of (4) emulsion; a small amount of a monomer having a hydroxyl group and performing polymerization, and then performing a neutralization to obtain a self-emulsified emulsion (Refer to Patent Documents 1 to 3.) Since the polymers contained in the emulsions are of high molecular weight, the adhesion between the formed film and the substrate is improved. If the polymer contained in the liquid is dried (4) into a film, it is difficult to dissolve n, and thus the redispersibility of the ink tends to be poor. [Prior Art Document] [Patent Document] [Patent Document 1] [Patent Document 2] Japanese Laid-Open Patent Publication No. Hei No. Hei 2-7-1679 Problem to be Solved The present invention has been made in view of the problems of the prior art, and it is an object of the invention to provide a printing which has excellent discharge stability and is excellent in both water resistance and adhesion to a substrate. The film can be re-dissolved and easily removed even if it is dried, etc. (4) Emulsion-type adhesive of ink ink 101108433 5 201243008, and a method for producing the same. Further, the object of the present invention is to provide : Inkjet film which has excellent discharge stability and can form a water-repellent coating and excellent adhesion to a substrate, and can be re-dissolved and easily removed even if it is dried by a discharge port (print head) Water-based pigment ink. (Means for Solving the Problem) The inventors of the present invention have intensively studied and found that a polymer block containing a high-concentration component and a water-insoluble A polymer block and a high-concentration carboxyl group-containing water are contained. The emulsion type binder of the acrylic block copolymer (AB block copolymer) composed of the B polymer block having high solubility can solve the above problem as a binder for forming a skin of the ink. The problem is solved by the present invention shown below. According to the present invention, an emulsion type adhesive is provided, and 90% by mass or more of the constituent components are (meth)acrylate monomers and contain A. The polymer embedded B aB , the Α_Β block copolymer has a number average molecular weight of 5,000 〜1 〇〇, 〇00, and the molecular weight distribution (weight *average I amount / number average molecular weight) is 1.7 or less; The acid value of the ruthenium polymer block is 〇~3〇mgK〇H/g, and the glass transfer point is below 〇C. The acid value of the above B polymer block is 75~25〇mgK〇H/g; The AB enemy copolymer is neutralized by an alkali substance and self-energized in an aqueous medium to form emulsion particles having a number average particle diameter of 3 〇 to 3 〇〇 nm. Further, according to the present invention, an aqueous inkjet ink for inkjet ink is provided, which is a binder for forming a pigment and a film, and is characterized in that the adhesive for forming a film is the emulsion adhesive described above. . In the present invention, it is preferred that the above pigments are derived from dye index numbers (ci) Pigment Blue-15:3 and 15:4; CI Pigment Red-122 and 269; CI Pigment Violet-19; CI Pigment Yellow-74, 155, 180 and 183; CI Pigment Green-7, 36 and 58; CI Pigment Orange-43; CI Pigment Black-7; and at least one selected from the group consisting of CI Pigment White-6, and the average number of primary particles is not full 350 nm; The content ratio of the above-mentioned pigment is 4 to 15% by mass based on the total amount of the ink (100% by mass), and the content of the binder for forming a film is 5 to 20% by mass. Furthermore, according to the present invention, there is provided a method for producing an emulsion type adhesive, which is characterized by comprising: at least an iodine compound used as a polymerization starting compound, The step of synthesizing the above-mentioned AB block copolymer by subjecting a methyl group acrylate monomer to living radical polymerization. In the present invention, a group of phosphorus compounds composed of a phosphorus halide, a phosphite compound, and a phosphinate compound, a group of nitrogen compounds composed of a quinone imine compound, and a phenol system are preferable. a group of oxygen compounds composed of a compound; and at least one compound selected from the group consisting of a hydrocarbon compound group composed of a diphenylnonane compound and a cyclopentadiene compound is used as a catalyst, and The above AB block copolymer was synthesized. Further, the polymerization temperature in the case of performing the living radical polymerization is preferably 30 to 50 °C. In the present invention, it is preferred to carry out the above-mentioned activity-free polymerization in a water-soluble organic solvent, and then add the test substance for neutralization, followed by mixing with water to self-emulsifie the above-mentioned A-B block copolymer. (Effect of the Invention) The specific block copolymer contained in the emulsion type adhesive of the present invention does not dissolve when it exists in the ink, and can exist as particles. Therefore, when the emulsion type adhesive of the present invention is used, it is possible to provide an aqueous inkjet ink for inkjet which has low viscosity, excellent discharge stability, and can be printed at high speed. Further, by using the emulsion type adhesive of the present invention, it is possible to prepare an aqueous inkjet ink for ink jet which can form a print film having water resistance and excellent adhesion to a substrate such as paper or film. Further, by using the emulsion type adhesive of the present invention, it is possible to prepare an aqueous inkjet ink for inkjet which can be re-dissolved and easily removed (having resolvability) even when the discharge port (print head) is dried. [Embodiment] 1. Emulsion type adhesive Hereinafter, the details of the present invention will be described by way of an example for carrying out the invention. The polymer contained in the emulsion-type adhesive of the present invention is an A-B block copolymer in which 90% by mass or more of the constituent components are (mercapto) acrylate monomers. The A-B block copolymer has a number average molecular weight of 5,000 to 100,000, and a molecular weight distribution (weight average molecular weight / number average molecular weight) of 1.7 or less. Further, the A-B block copolymer contains an A polymer block and a B polymer block. The A polymer block has an acid value of 0 to 30 mgKOH/g, a glass transition point of 00 ° C or less, and is substantially insoluble in the polymer block of 101108433 8 201243008 water. Further, the B polymer block is a polymer block which is substantially water-soluble in an acid value of 75 to 250 mgKOH/g. The A-B block copolymer is 90% by mass or more, preferably 7% by mass or more of the constituent component of the A-B block copolymer. The (mercapto) acrylic vinegar-based single system can be used in the prior art, and is not particularly limited. Specific examples of (meth)acrylic acid-based monomers, such as K-methyl dilute vinegar, (mercapto) acrylic acid, and aliphatic or alicyclic groups. (meth) propylene ketone; (meth) acrylic acid vinegar, (mercapto) acrylic acid acetoacetate, etc. (Methyl) propylene acrylate, methoxy ethoxy acetate, (meth) acrylic acid ethoxy ethoxylate, (methyl) propylene cyclization (four) or more) (曱) acrylic acid pure vinegar, (meth) acrylate, etc., hydroxyl-containing (fluorenyl) (tetra) vinegar; (meth) dimethyl methacrylate, (methyl) bis(acid) Amino-based (ethyl) acetoacetate such as diethylaminoacetic acid vinegar; (methyl) propionic acid ring propylene, (meth) acrylic acid tetrahydrogen, (mercapto) acrylic acid Oxetane is an isobaric acid methyl) yttrium methacrylate acrylate, U, 2, 2 _ tetra ethane oxime, etc. gas: sub (Methyl methacrylate) vinegar; end (methyl) Stupid ethyl amide monomer Giant monomer, hexyl red monomer; methyl propyl _ 2_[3 tuned benzotrisyl 2 thiol phenyl] ethyl, (meth) acrylate 3, 3, 5, 5 • A (meth) acrylate or the like which enhances light resistance, such as tetramethylpiperidine. The addition of 90% by mass or more of the constituent component to the (meth)acrylic acid-based monomer may also be followed by "other silking monomer" and (?) propylene _ 9 101108433 201243008 monomer - and use. As the "other addition polymerization monomer" specific "! Examples of the benzoic acid, ethionyltoluene, (meth)acrylamide-based monomer (mercapto) acrylonitrile-based monomer, and sulphuric acid ethyl vinegar-based monomer may be mentioned. The acid number of the A B copolymer is within a specific range of values. Therefore, as a monomer constituting the A B silk material, (d) is a (mercapto) acryl-based compound having an acid group. Examples of the acid group include a thiol group, an acid group, and an acid-decomposing group. Among them, from the viewpoint of water resistance and ease of availability, it is preferred to use a repellent (meth)acrylic acid compound. Examples of the (meth)acrylic acid compound having a money base include (meth)acrylic acid, acrylic acid dimer, itaconic acid, maleic acid, dicarboxylic acid, crotonic acid, acid donating or A monomer obtained by semi-esterifying a hydroxy group-containing monomer such as a monobasic acid with a hydroxy group such as 2-hydroxyethyl (meth) acrylate. Among them, from the viewpoint of polymerizability, it is particularly preferred to be (mercapto)acrylic acid. Next, the A polymer block and the B polymer block constituting the A-B block copolymer will be separately described. Further, the A_B block copolymer is a block copolymer in which two blocks are bonded, and for convenience, one of the polymer blocks is referred to as "A polymer block", and the other is called " B polymer block". (A polymer block) The A polymer block is a polymer block obtained by appropriately polymerizing the above various monomers. The acid value of the A polymer block is 〇3 〇mgK 〇H/g, preferably 0 to 20 mgKOH/g. Since the acid value is in the above range, the a polymer block is substantially insoluble in water. Therefore, when the 101108433 10 rs 201243008 A_B money-filled material containing the A polymer block is dispersed in the aqueous medium towel and is subjected to emulsion formation, it is considered that the A polymer block system will become the portion 1 of the particle formation. In the acid value range, the A polymer block contains a small amount of acid groups, and the v, the substrate, the connectivity, and the particle size of the emulsion particles can be adjusted. The glass transition point (hereinafter also referred to as ",") of the A polymer stagnation section is preferably: 5 to 5 Å. 〇 Since the Tg is in the above range, the film-forming property of the emulsion type adhesive is improved. More preferably, the Tg is room temperature (25. 〇 or less, and if U is 6 〇C or less, the film forming property can be improved by adding a creator or the like to the ink. The Tg system of the A polymer block can be used in the A polymer. After the block is polymerized, it can be easily measured by thermal analysis. For example, when a polymer (silk) which is copolymerized with a monomer of the X component is used, the quality of each monomer is obtained. (g) Assuming that "Wi, W2, · · .Wx", the Tg (°C) of the homopolymer of each monomer is assumed to be "Ding, τ2, · · · · T port main Αχ", then The Tg(T(°c)) of the copolymer can be calculated from the following formula (1): l/T=Wl/(Tl+273)+W2/(T2+273)+ · · · Wx/(Tx+ 273) · (1) The Tg value of the homopolymer may be the value described in the "Handbook of Polymers 4th Edition", and the values of various literatures may be used. The value described in the edition. By the presence of the A polymer block, the AB block copolymer is particleized and substantially insoluble in water. Therefore, the viscosity of the emulsion type binder containing the AB block copolymer is lowered. .therefore, The emulsion type adhesive is added to the black water. 'The viscosity of the ink is still not rising, and the ink discharge stability is good. 101108433 11 201243008 Also, since the AB block copolymer is substantially insoluble in water, it is contained in the use. The ink of the emulsion type adhesive of the AB block copolymer can form a printing film having high adhesion to the substrate. (B polymer block) The acid value of the B polymer block is 75 to 250 mgKOH/g. Preferably, it is 100 to 200 mgKOH/g. Since the acid value is in the above range, the B polymer block is substantially soluble in water. If the acid value of the B polymer block is less than 75 mgKOH/g ', it is redissolved. On the other hand, if the acid value of the b polymer block exceeds 250 mgKOH/g, the water resistance of the formed printing film may be poor. In addition, by the acid in the B polymer block The base is neutralized by the test substances such as ammonia, amine, sodium hydroxide, etc., and the B polymer segment becomes a polymer block soluble in water. When the A polymer block is subjected to particle formation, the B polymer block Will dissolve in water. Thereby, the particle size of the block copolymer will be affected. By controlling, the particles of the AB block copolymer can be stably present (dispersed) in the aqueous medium. Further, the inkjet water-based pigment ink prepared by using the ruthenium-tantalum block copolymer, even if the print head is dried, It is still possible to utilize the high water solubility of the ruthenium polymer block to exhibit excellent resolubility. The acid groups in the ruthenium polymer block are neutralized in the ink. Therefore, the ruthenium polymer embedded & It is a soluble block. Therefore, an ink using an emulsion type binder containing an A-fluorene block copolymer of a hetero-polythene block can be used even if the soil d (print head) is dry. The washing liquid such as water is easily dissolved to exhibit excellent redispersibility. 101108433 12 201243008 (A-B block copolymer) The number average molecular weight (hereinafter also referred to as "Mn") of the A-B block copolymer is 5,000 to 100,000, preferably 8,000 to 5 Å, 〇〇〇. Further, Μη is a polystyrene-converted value measured by a gel permeation chromatography analyzer (hereinafter also referred to as "GPC") unless otherwise stated. The ΜηΑ polymer block of the Α_Β block copolymer is Μη, in combination with the Mn polymer block Mni. Therefore, the respective Μ&> of the Α polymer block and the ruthenium polymer block are not particularly limited until the Μη of the A-B segment copolymer is within the above numerical range. If the Μη of the ruthenium-iridium block copolymer is less than 5, 〇〇〇, since the molecular weight is too small, physical properties such as adhesion of the printing film formed by using the water-based pigment ink for inkjet are hard to be improved. On the other hand, if the ?n of the ?-? block copolymer is too large, it is impossible to impart resolubility to the inkjet aqueous pigment ink. The molecular weight distribution (hereinafter also referred to as "PDI") expressed by the weight average molecular weight (hereinafter also referred to as "Mw") of the Α-Β block copolymer, and the ratio (Mw/Mn) of the logarithmic average molecular weight (?η) is 1.7. The following, better! 6 or less. The mass ratio of the A polymer block to the b polymer rice section contained in the copolymer is preferably A/B=20/80 to 95/5, more preferably a/B=30/70~ 90/10. If the mass ratio of the A polymer block to the B polymer block is within the above range, the water-insoluble portion (A polymer block) of the AB block copolymer and the water-soluble portion (B polymer segment) are formed. The balance is good. The A-B block copolymer is, for example, obtained by polymerizing one of the polymer blocks, adding a monomer component constituting the other polymer block, and further synthesizing by polymerizing 101108433 13 201243008. Here, if the PDI of one of the polymer blocks which has just started the polymerization is large, the PDI of the other polymer block which is subsequently polymerized becomes larger. If the PDI of the obtained A-B block copolymer is too large, the emulsion formation of the A-B block copolymer tends to be difficult, and the resolubility of the inkjet aqueous pigment ink tends to be insufficient. Therefore, the AB block copolymer can be well emulsioned by previously reducing the PDI of one of the polymer blocks which has just started polymerization to a certain extent, so that the pdi of the finally obtained AB block copolymer is less than 1.7. And can improve the re-solubility of inkjet water-based pigment inks. (Emulsion-type adhesive) The emulsion-type adhesive of the present invention is an A-B block copolymer which is neutralized by an alkali substance and emulsified by itself in an aqueous medium to form emulsion particles. Further, the number average particle diameter of the emulsion particles to be formed is 30 to 300 nm, preferably 50 to 200 nm. If the number average particle diameter of the emulsion particles is less than 3 〇 nm, the emulsion particles may be too fine, resulting in an increase in the viscosity of the ink. On the other hand, if the number average particle diameter of the emulsion particles exceeds 300 nm, the ink jet head tends to be clogged, which may cause difficulty in discharge. For example, the A-B block copolymer is added directly or temporarily after the polymerization, and an alkali substance is added to the aqueous medium to neutralize the acid groups of the A_B block copolymer. Since the A polymer block is a substantially water-insoluble block, it contributes to the granulation of the A-B block copolymer. On the other hand, since the B polymer block belongs to a substantially water-soluble block, the 101108433 201243008 AB block copolymer is self-emulsified (4) to form a stable emulsion particle number. , the number of average inventions invented _%_ ♦ as measured. This device (for example, the product name ", coffee", and the size of the particle are measured. For the measurement of the acid group of the copolymer, the amount of the copolymer is particularly limited, for example, ammonia. <Alkaline substance' There is no organic amine such as an amine, sodium hydroxide hydroxide $ female, methylaminoethanol, triethanol, and oxygen-secret surface. Further, in the above water system, the tannin system may be water alone or a mixed solvent of an organic solvent. = water as a water-soluble organic solvent = exemplified by water-soluble low-grade aliphatic alcohols such as ethanol and isopropanol; r:r:_ can be one (10) = alcohol-I-methyl water-soluble solvent; propylene glycol Glycol and its early (four) and other water-soluble diol-based solvents; Ν · water-soluble 醯 (iv) solvent; glycerin, 仏 二 二 二 二 二 二 二 二 二 二 二In addition, these water-soluble organic solvents may be used alone or in combination of two or more. Further, the amount of the water-soluble organic solvent used in combination with 6" and m ^ kg is arbitrary. The emulsion type spotting agent of the present invention is preferably obtained by polymerizing the AB submerged silk material in a water-soluble organic solvent, (1) Adding the aqueous solution of (4) to neutralize the acid hydrazine of the AB block copolymer to prepare itself by emulsification, or (9) adding the test substance and adding the water to the Α Β Β 丝 丝 四 四 俾 俾By modulating the emulsion residual agent accordingly, 101108433 201243008 can achieve micronization without precipitation and thickening. 2. Inkjet water-based pigment ink. Secondly, the ink-jet water-based pigment of the present invention is used. The inkjet water-based pigment ink of the present invention contains a binder for forming a pigment and a film, and the binder for forming a film is the emulsion-type adhesive. The emulsion-type adhesive is used. In the case of a binder for forming a film, it is possible to form a print film having high-speed printability and excellent discharge stability, and excellent in water resistance and adhesion to a substrate. An ink-jet aqueous pigment dispersion ink which can be re-dissolved and easily removed by drying, such as a discharge port (print head), etc. The ratio of the emulsion-type binder contained in the ink-jet aqueous pigment ink of the present invention is relatively The total amount of the ink (100% by mass) is preferably 5 to 20% by mass, more preferably 7.5 to 15% by mass, based on the solid content. (Pigment) The pigment may be an organic pigment or an inorganic pigment which has been conventionally used. Two or more types may be used alone or in combination. Specific examples of the pigment include carbon black pigment, quinophthalone pigment, indigo pigment, and benzimidazole pigment isoindolinone pigment. An azo pigment, a titanium oxide pigment, etc. wherein the 'pigment is preferably a dye index number of the pigment used in the inkjet ink, such as Shima (CI) Pigment Blue-15:3 and 15:4; CI·Pigment Red_122 and 269 ; q Pigment Violet·19; CI Pigment Yellow-74, 155, 180 and 183; CI, Pigment Green _7, 36 and 58; CI Pigment Orange-43; CI Pigment Black-7; and cj Pigment White 6 Select at least one of the groups. 101108433 201243008 The average primary particle diameter of the material is preferably less than 350 nm, and the organic pigment is preferably 150 nm or less. Especially when the pigment system is CI pigment blue long 15 · 4; CI pigment red-122 and 269; CI·pigment purple _ 19; C.1. Pigment Yellow-74, 155, 180 and 183; CI Pigment Green-7, 36 and 58; ci Pigment Orange _43; and c丄 Pigment Black _7, the number of such pigments is averaged once The polar diameter is preferably 150 nm or less. Further, in the case where CX Pigment White·6 is used as the pigment, the amount of the CI Pigment White-6 is preferably 3 nm or less. In particular, in consideration of the blockage of the print head and the sharpness of the formed image, the smaller the number average primary particle diameter, the better. The pigment may be a self-dispersible pigment having a functional group introduced into the surface thereof, or may be a pigment which is subjected to treatment such as surface treatment or transcapsulation using a surface disintegrator such as a coupling agent. Further, the ratio of the pigments in the ink-based aqueous pigment ink is 'relative to the total amount of the ink (1 GG% by mass), preferably 2 to 15 〇 / 贝 berry / 〇, more preferably 4 〜 10% by mass. (Pigment Dispersant) Among the ink aqueous pigment inks, a pigment dispersant is preferably contained. In particular, the pigments are preferably not self-dispersible pigments, because when pigments (inorganic pigments, organic pigments) which do not have self-dispersion = are used, the pigments can be adapted to the field and the knife Preferably. The pigment dispersant can be used in the past, and is not particularly limited to & Specific examples of the pigment dispersant include a random polymer such as a propylene fluorene-based U-styrene polymer, a copolymer type 101108433, a 201243008 dispersant, a graft polymer-type dispersant, and a star polymerization. Type dispersant branch dispersant and the like. Further, the proportion of the dispersing agent contained in the aqueous ink for ink of the nozzle ink is 0.5 to 15% by mass, more preferably 2 to 2% with respect to the total amount of the ink (100% by mass) relative to the black > 1〇% by mass.乂 乂 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( The "other components" may be exemplified by a water-soluble organic solvent such as water. Specific examples of the solvent of the water-soluble machine include diethylene glycol alone, triethylene dibutyl ether, glycerin, propylene glycol, 1 2 ρ - , G-alcohol, and 2-° ratio. Each sigma ketone, methyl-2- ketone, and the like. By using these water-soluble organic solvents, the drying of the print head can be more effectively prevented. Further, it is preferable to use a water-soluble organic solvent such as _ or more, preferably in combination with water. The ink in the mouth is contained in the ink (4). The ratio of the water-soluble "H organic (four)" is preferably from 1 to 40 by mass based on the total amount of the ink (10% by mass). /0, more preferably 5 to 2% by mass. Specific examples of the various additives include a surfactant, a pigment wood, a leveling agent, an antifoaming agent, and an ultraviolet absorber. The content ratio of the additives is not particularly limited as long as it does not impair the effects of the present invention. 3. Method for Producing Emulsion-Based Adhesive Next, a method for producing an emulsion-type adhesive will be described. 101108433 201243008 The invention discloses a method for producing an emulsion type adhesive, comprising: using at least an iodine compound as a polymerization starting compound 'a living radical polymerization of a (fluorenyl) acrylate monomer) to synthesize AB block copolymerization The steps of the object. Hereinafter, the details will be described. (Synthesis step of A-B block copolymer) The A-B block copolymer can also be synthesized by a conventional living radical polymerization method. However, in the present invention, the A-B block copolymer is synthesized by living radical polymerization of the above (meth) acrylate monomer. In addition, when a living radical polymerization is carried out, an iodine compound is used as a polymerization starting material - an iodine compound is used as a polymerization starting compound, and a base derived from heat or light is reacted with a monomer to generate a reaction. The polymer is too iodine from 7 to no free radicals. Since the successively generated iodine radicals are anchored to the free end of the polymer end, the termination reaction can be prevented. Since the living radical polymerization is carried out by the difficult reaction, the molecular weight and structure of the obtained & ^ The iodine compound is mentioned before it can be produced by the action of heat or light, and the rest is not particularly limited. Specific examples of the tantalum G 5 substance include a 2-base phenyl group, a phenyl group, and the like; a 2-cyano-2-iodopropane, a 2-cyano group 2_ A cyano group-containing moth compound such as iodine butane, 1-iodocyclohexane, 2-cyano-2-pentane valeronitrile, and the like. The commercially available compound may be used as it is, or a compound synthesized according to a conventionally known method may be used, and the compound may be obtained by, for example, reacting with an anthracene compound such as azobisisobutylpyr 101108433 19 201243008. . Further, an organic dentate having a halogen atom other than hard, and a quaternary ammonium halide, sodium hydride, or the like may be used, and a halide salt may be generated in the reaction system to generate a hydrazine exchange reaction. Compound. Further, in the case of living radical polymerization, it is preferred to use a catalyst which can remove a ruthenium atom from a moth compound to form a disk radical. Examples of such a catalyst include a base compound such as a halogenated lin, a phosphite-based compound, or a phosphinic acid sulfonate compound, and an oxygen-based compound such as a nitrogen compound or a genus compound such as a quinone imine compound; A hydrocarbon compound containing an active carbon atom such as a brothel compound or a cyclopentanyl compound. Further, these catalysts may be used alone or in combination of two or more. ~ Specific examples of the squara compound include three-breaking dish, squaric acid diacetate, di-n-butyl sulphate, ethoxyphenylphosphinic acid, phenylphenoxy-human phosphine Acid g is intended. Specific examples of the nitrogen-based compound include: ketoneimine, 2,2-dimercaptosuccinimide, cis-butylimine, imine, and N-iodoammonium. Amine, intramethylene urea, and the like. Specific examples of the oxygen-based compound include hydrazine, hydrogen, methoxyhydrogen, third butyl, catechin, and di-tert-butyl toluene. Specific examples of the hydrocarbon compound include cyclohexadiene, triphenyl fluorene, and the like. The amount of catalyst used (molar number) is less than the amount of polymerization initiator used (mole number) <3 If the amount of the catalyst used is too large, it may be difficult to carry out polymerization. The temperature at the time of living radical polymerization is preferably set to 3 Å to 咐. JP 101108433 20 201243008 In the case where thioglycolic acid is used as the (mercapto)acrylic acid compound having an acid group, it is preferred that the temperature at which the living radical polymerization is carried out is set within the above temperature range. If the temperature is too high, the polymerization terminal _ radical will easily decompose due to the 浠 浠 夂 ,, and the end of the formed polymer will be unstable, which may make the living radical polymerization difficult. When the living radical n-radical polymerization is carried out, in order to make it easier to generate a hydrazine radical, it is preferred to add a polymerization initiator. As the polymerization initiator, an azo-based initiator and a peroxidized (tetra)-based conventionally known compound can be used. However, the polymerization initiator is preferably a compound which can sufficiently generate a hard radical at the above polymerization temperature. Specifically, it can be exemplified by: 2,2,-azobis(4)decyloxy-2,4-dimercaptophthalonitrile), etc.聚合.001~ο.1 molars of the polymer, better set to 〇.〇〇2~〇.〇5 moles. If the amount of the polymerization initiator used is too small, there will be a situation in which the living radical polymerization cannot be sufficiently ordered. In addition, if the amount of the silk-initiator used is too large, there may be no self-twisting. , 岐 · · it (four) free silk cooperation as a possibility of side effects. The living radical polymerization may also be a bulk polymerization using no organic solvent, but it is preferred to use a solution polymerization of the A agent. The solvent is preferably a soluble compound, a catalyst, a monomer, and a polymerization starting solvent. Among them, in view of dispersing the pigment, a water-soluble organic solvent is preferred. When the solution polymerization is carried out, the polymerization concentration (monomer concentration) is not particularly limited, and is preferably 5 to 8 Gf%, more preferably 20 to 10101. If the concentration of the form is less than 5% by mass, the monomer concentration is too low, and there is a possibility that the polymerization is not completed. On the other hand, if the solid content concentration exceeds 8 〇% by mass, the bulk polymerization proceeds substantially, and the polymerization degree becomes too high. Therefore, there is a tendency that the stirring tends to be difficult and the polymerization yield is lowered. The living radical polymerization is preferably carried out until the monomer disappears. Specifically, the polymerization time is preferably set to 0.5 to 48 hours, and substantially more preferably set to ... hours. Further, the polymerization environment is not particularly limited, and may be an environment in which oxygen is present in a normal range, or a nitrogen gas flow environment. Further, the material (single body or the like) used in the polymerization may be subjected to inspection, activated carbon treatment, or oxidation reduction to remove impurities. Further, the polymerization may be carried out under (4), or may be carried out in a transparent container such as glass. Next, the order of aggregation will be described. The polymerization sequence of the A_B block copolymer is preferably (1) after the hydrophobic monomer is polymerized to form the A polymer block, and (ii) the monomer constituting the B polymer block is added, and further polymerization is carried out. If the monomers constituting the B polymer block are polymerized first, polymerization will be incomplete, resulting in? The propylene propylene (4) has a single singularity in the reaction system. In this case, the monomer having an acid group is easily introduced into the A polymer block, and the hydrophobicity of the formed A polymer block (causing the acid value to exceed a predetermined range) may be impaired. On the other hand, when the monomer constituting the A polymer block is polymerized first, even if the polymerization is not completed and the monomer remains in the reaction system, the mass of the constituent component of the ruthenium block copolymer obtained is 90. The AB block copolymer can be easily obtained by introducing the polymer block into a polymer block of (meth)acrylic acid g as a monomer. The molecular weight of the obtained rhodium-iridium block copolymer can be controlled by adjusting the amount of the polymerization starting compound (iodine compound) used. Specifically, Α_Β纽共(四) of any molecular weight can be obtained by the number of moles of the local monomer in comparison with the number of the starting compounds of the polymerization starting compound. For example, when the polymerization starting compound ' of the oxime is used and the monomer having a molecular weight of the megamolar is used for polymerization, an A B copolymer having a theoretical molecule of "lx (10) x 5 GG = 5 q, _" can be obtained. Namely, the theoretical molecular weight of the A_B block copolymer can be calculated by the following formula (2). In addition, the above-mentioned "molecular weight" coefficient is a concept in which the average knife setting (] \411) and the weight 1 average molecular weight (Mw) are included. "Theoretical molecular weight of the AB block filament" = "polymerization starting compound ι Moer" X "monomer molecular weight" x "molar number of monomer / molar number of polymerization starting compound" · · · (2) Further, in the case of the above-described tetraradical polymerization, there is a case where the derivatized two molecules are prevented from being deuterated, and thus the ruthenium-tellurium block copolymer having the above theoretical molecular weight may not be obtained. The block copolymer is preferably obtained in the absence of such a 4 reaction. However, it is also possible to increase the molecular weight of the ruthenium/ruthenium block copolymer which is obtained by the coupling, and it is also possible to reduce the molecular weight of α·β New Zealand (4) which is obtained by stopping the money in the polymerization reaction. Further, the polymerization rate may not be 100%. Further, a polymerization agent or a catalyst may be added at the end of the polymerization, and the polymerization may be completed. The β卩' can be formed as long as it can form a ruthenium-tellurium block copolymer. 101108433 23 201243008 The obtained a-B block copolymer maintains a state in which an iodine atom derived from an iodine compound used as a polymerization starting compound is bonded, but preferably the iodine atom is detached. The method of separating the shoulder from the A-JB block copolymer is carried out before the conventionally known method, and the rest is not particularly limited. Specifically, it is necessary to ride on the heat of the Α·Β block wire and to correct the money. Further, the ruthenium-tellurium block copolymer may be treated by sodium thiosulfate or the like. The detached rhyme, the _activated carbon, and the oxidized material Wei attaching agent are treated and removed. An emulsion type binder containing an emulsion particle having a number average particle diameter of 30 to 30 Å can be obtained by self-emulsification using an aqueous test substance and a lyophilized Α Β block in the aqueous medium. Further, in the present invention, it is preferred that the living radical polymerization (9) is carried out in a water-soluble organic solvent (9). Then, the test substance is added to the reaction system to be neutralized, and (iii) is then mixed with water. The A_B block copolymer is self-emulsified. Thereby, the number average particle diameter of the shaped Wei I material can be easily adjusted. 4' Method for Producing Inkjet Water-Based Pigment Ink A method for producing an aqueous inkjet ink for inkjet will be described. The Kf raw pigment ink for the spray 1 is obtained by, for example, (1) dispersing the pigment in a pigment dispersion in an aqueous medium, and (9) adding the obtained dispersion to the emulsion type, and adding an additive or the like as needed. Manufacturing. The pigment dispersion system can be prepared by a conventionally known method. For example, a pigment dispersion can be obtained by simply mixing a pigment_dispersant and a hydrazine medium, and adding an additive such as a reagent 101108433 ΓΘ 24 201243008 as needed. When the pigment is an organic pigment, the ratio of the organic pigment contained in the pigment dispersion is preferably 10 to 30% by mass based on the total amount of the ink. Further, when the pigment is an inorganic pigment, the ratio of the inorganic pigment contained in the pigment dispersion is preferably 40 to 70% by mass based on the total amount of the ink. The proportion of the pigment dispersant contained in the pigment dispersion is preferably 5 to 30 parts by mass based on 1 part by mass of the pigment. Further, when the pigment is a self-dispersible pigment, a pigment dispersant may not be used. When the components are mixed to disperse the pigment, for example, a kneader, a twin roll machine, a three-roller, a MIRACLE KCK (trade name manufactured by Asada Steel Co., Ltd.), a kneading machine, an ultrasonic wave disperser, and a microjet can be used. Homogenizer (product name, manufactured by Mizuho Co., Ltd.), particle machine (product name, manufactured by Yoshida Machinery Co., Ltd.), Star Burst (product name manufactured by Sugin〇Machine Co., Ltd.), G_smasher (product name manufactured by Ruigus Co., Ltd.), high-pressure homogenization machine. Further, a ball mill, a sand mill, a horizontal grinding medium disperser, a colloid mill, or the like may be used. In consideration of the color developability of the ink, the print quality, and the sedimentation of the pigment in the ink, etc. When the organic pigment is used, the number average particle diameter of the organic pigment in the pigment dispersion is preferably i5 Q nm or less. Further, when inorganic _ is used, the number average particle size of the inorganic lung in the surface dispersion is preferably 300 nm or less. In addition, in order to obtain a pigment dispersion in which a pigment is dispersed according to a desired particle size distribution, for example, a size of a pulverizing medium of a small disperser, (9) an increase of a filling rate of the pulverizing medium, (10) an extension of the treatment time, and (4) a reduction of 101,108,433 • Λ 25 201243008 Slow discharge speed, (V) pulverized, and then grading by means of filters, centrifugal separators, etc. Also, these methods can be combined. Further, a pigment which has been previously ground by a conventionally known method such as a salt milling method can also be used. After the components are mixed and dispersed, it is preferred to remove coarse particles by means of a centrifugal separator or a filter. The inkjet water-based pigment ink of the present invention can be obtained by mixing the obtained pigment dispersion, an aqueous medium, an emulsion-type binder which is a binder for forming a film, and an additive which is optionally used, according to a usual method. . From the viewpoint of expanding the dot diameter of the inkjet printing to the optimum width, the surface tension of the inkjet ink is preferably 20 to 40 rnN/rne for the surface tension of the inkjet ink for inkjet. In the above numerical range, it is preferred to add a surfactant to the inkjet water-based pigment ink. As the surfactant, a conventionally known one can be used. If the amount of the surfactant added is too large, the dispersion stability of the pigment may be impaired. Therefore, the ratio of the surfactant contained in the aqueous ink for inkjet ink is preferably 001 to 5% by mass, more preferably 0.1 to 2% by mass. The viscosity of the aqueous inkjet pigment ink of the present invention is not particularly limited, and when an organic pigment is used, it is preferably 2 to 1 mPa·s. Further, in the case of using an inorganic pigment, it is preferably 5 to 30 mPa·s. [Examples] Next, the examples and comparative examples are given to more specifically explain the present invention. However, the invention is not limited by the examples. In addition, both "parts" and "%" in the text are based on quality. 〇Π〇8433 26 201243008 (1) Preparation of emulsion type adhesive (Example 1: Preparation of emulsion type adhesive (1)) It is equipped with a mixer, a reflux condenser, a thermometer, and a nitrogen introduction tube. In the flask, charged with: diethylene glycol dioxime (hereinafter referred to as "DMDG") - I31.7 parts, 1.0 part of iodine, 2,2'-azobis(4-decyloxy-2, 4-dimethylvaleronitrile (hereinafter referred to as "V-70") 4.9 parts, 44 parts of benzyl methacrylate (hereinafter referred to as "BzMA"), and hydroxyethyl methacrylate (hereinafter referred to as "Hema" ” 13 parts, and Ν·峨 拍 拍 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 The mixture was stirred and heated to 4 (rc, and polymerization was carried out. After 3 hours, the brown color of iodine disappeared. From this time, iodine was reacted with v_7 hydrazine, and it was confirmed that an iodine compound (polymerization starting compound) was formed in the reaction system. The temperature was kept constant, and after further polymerization for 4 hours, the solution of the A polymer block was obtained by natural cooling. A part of the solution was sampled, and the solid content concentration was determined to be 27.5%. The polymerization rate calculated by the concentration was about 85%. Further, the A polymer block was analyzed by GPC, and the result was 7, and the lion and PDI were 1.31. The composition of the obtained A polymer block. BzMA /HEMA= 77/23, calculated by theoretical calculation of the Ding system. 54.2 ° C, the acid value is OmgKOH / g. The part of the sampled solution is added to the water's result, there will be resin precipitation. It was confirmed that the obtained A polymer block was a substantially water-insoluble polymer. Methyl methacrylate (hereinafter referred to as "MMA") was added to the obtained solution of the A polymer block. 52.8 parts, methacrylic acid (hereinafter referred to as "MAA") 101108433 27 201243008 12.9 parts, and ν-70 0.45 parts of the mixture was subjected to polymerization for 4.5 hours to form a ruthenium polymer block, and a solution of the ruthenium-iridium block copolymer was obtained. The polymerization rate was about 100%. The structure of the ruthenium polymer block contains a constituent unit derived from BzMA and ruthenium belonging to the residual monomer. The conversion from the yield Β. The composition of the polymer block is ΜΜΑ/ΜΑΑ/residual monomer and 71/17 Further, the acid value of the ruthenium polymer block calculated from the content of ruthenium was 110 mgKOH/g. The Mn system of the obtained A-seven block copolymer was 14, and the PDI system was 1.45. Adding phenol as an indicator in a sample obtained by dissolving 5 parts of the sampled A_B block copolymer in 5 parts of toluene/ethanol (volume ratio)
醜利用0.1N的koh乙醇溶液施行中和滴定。結果，A-B 嵌段共聚物的酸值係69.〇mgKOH/g。又，從聚合產率的結 果所計算出之A聚合減段與β聚合健段的f量比係 A/B=39.5/60.5。 激烈搜拌A-Β嵌段共聚物的溶液，添加氨水1〇份與 水10伤的混合液，結果可獲得具黏性的半透明液體。若徐 緩添加水243.4份’便可獲得若干偏黃且具透明性的低黏度· 乳液(乳液型黏合劑⑴)。經利用B型黏度計所測定之低黏度- 乳液的黏度係85.5时a. s，固形份濃度係24 6%。又，利用 光散射粒度分佈測定機所測定之乳液粒子的數量平均粒徑 係 86nm。 (貫施例2 :乳液型黏合劑(2)之調製） 101108433Neutralization titration was carried out using a 0.1 N solution of koh ethanol. As a result, the acid value of the A-B block copolymer was 69. 〇 mgKOH/g. Further, the ratio of the amount of the A polymerization minus section to the β polymerization section calculated from the result of the polymerization yield was A/B = 39.5 / 60.5. The solution of the A-barium block copolymer was vigorously searched, and a mixture of 1 part of ammonia water and 10 parts of water was added to obtain a viscous translucent liquid. If 243.4 parts of water is added slowly, a number of yellowish and transparent low-viscosity emulsions (emulsion type adhesives (1)) can be obtained. The viscosity of the low viscosity-emulsion determined by the B-type viscometer was 85.5 a.s, and the solid concentration was 246%. Further, the number average particle diameter of the emulsion particles measured by the light scattering particle size distribution analyzer was 86 nm. (Example 2: Modulation of emulsion type adhesive (2)) 101108433
S 28 201243008 除 了使用 DMDG 362.3 份、碘 1.0 份、ν-70 4·9 份、MMA 105份、甲基丙烯酸2_乙基己酯（以下記為γ2ΕΗμα」）148.5 份、ΗΕΜΑ 45.5份、及二苯基曱烷0.17份之外，其餘均與 前述實施例1同樣地獲得Α聚合物嵌段的溶液。聚合率係 80.5°/。。所獲得之a聚合物嵌段的Μη係22,000，PDI係 1.56，聚合物組成係 ΜΜα/2εημα/ΗΕΜα-35/5〇/15，利用 理論計算所計算出的Tg係31.5。(：，酸值係OmgKOH/g。又， 將所採樣的溶液其中一部分添加於水中，結果有軟質聚合物 析出。藉此可確認到所獲得之A聚合物嵌段係屬於實質上 不溶於水的聚合物。 除了在所獲得之A聚合物嵌段的溶液中，添加MMA 40 份、MAA 17.2份、及V-70 0.6份的混合物之外，其餘均與 前述實施例1同樣地施行6小時聚合，形成B聚合物嵌段， 而獲得A-B嵌段共聚物的溶液。聚合率係約1〇〇。/(^從產率 所換算的B聚合物嵌段組成係MMA/MAA/殘留單體 与35Λ5/50。又，從MAA的含有量所計算出之B聚合物嵌 段的酸值係97.8mgKOH/g。 所獲得之A-B嵌段共聚物的Μη係28,000，PDI係1.67， 酸值係31.0mgKOH/g。又，從聚合產率的結果所計算出A 聚合物嵌段與B聚合物嵌段的質量比係A/B=67.5/32.5。激 烈攪拌A-B嵌段共聚物的溶液，添加二曱基胺基乙醇Π.8 份與水Π.8份的混合液，結果獲得帶有藍色的白濁狀高黏 101108433 29 201243008 性液體。添加水885.7份，結果獲得帶有藍色的低黏性白色 礼液（乳液型黏合劑(2))。經利用b型黏度計所測定之白色乳 液的黏度係44.9mPa · s，固形份濃度係26.3。/。。又，乳液粒 子的數量平均粒徑係153nm。 (實施例3 :乳液型黏合劑(3)之調製）S 28 201243008 In addition to using 362.3 parts of DMDG, 1.0 part of iodine, ν-70 4·9 parts, 105 parts of MMA, 2-ethylhexyl methacrylate (hereinafter referred to as γ2ΕΗμα) 148.5 parts, ΗΕΜΑ 45.5 parts, and two A solution of the ruthenium polymer block was obtained in the same manner as in Example 1 except that 0.17 parts of phenyl decane was used. The polymerization rate was 80.5 ° /. . The obtained polymer block had a Μ 2 system of 22,000, a PDI system of 1.56, and a polymer composition of ΜΜα/2εημα/ΗΕΜα-35/5〇/15, which was calculated by theoretical calculation of the Tg system 31.5. (: The acid value is OmgKOH/g. Further, a part of the sampled solution was added to water, and as a result, a soft polymer was precipitated. It was confirmed that the obtained A polymer block was substantially insoluble in water. The polymer was applied in the same manner as in the above Example 1 except that a mixture of MMA 40 parts, MAA 17.2 parts, and V-70 0.6 parts was added to the obtained A polymer block solution. Polymerization to form a B polymer block, and a solution of the AB block copolymer is obtained. The polymerization rate is about 1 〇〇. /(^ The B polymer block composition is MMA/MAA/residual monomer converted from the yield. Further, the acid value of the B polymer block calculated from the content of MAA was 97.8 mgKOH/g. The obtained AB block copolymer had a Μ 2 system of 28,000, a PDI system of 1.67, and an acid value system. 31.0 mgKOH/g. Further, the mass ratio of the A polymer block to the B polymer block was calculated from the result of the polymerization yield, A/B = 67.5 / 32.5. The solution of the AB block copolymer was vigorously stirred, and added. a mixture of 8 parts of decylaminoethanol hydrazine and 8 parts of hydrazine. The result is a white turbid high viscosity 101 with blue color. 108433 29 201243008 Sex liquid. Adding 885.7 parts of water, the result is a low-viscosity white liquid with blue color (emulsion type adhesive (2)). The viscosity of white emulsion measured by b-type viscometer is 44.9mPa. · s, the solid concentration is 26.3%. Further, the number average particle diameter of the emulsion particles is 153 nm. (Example 3: Preparation of emulsion type adhesive (3))
除 了使用 DMDG 197.1 份、碘 〇 4 份、V-70 2.4 份、MMA 54份、甲基丙烯酸丁酯（以下記為「BMA」）49份、甲基丙 烯酸十二烷基酯（以下記為rLMA」）5〇份、MAA3份、及 一第二丁基羥甲苯（以下記為「ΒΗτ」）〇,丨份，施行6小時 聚合之外’其餘均與前述實施例1同樣地獲得A聚合物嵌 段之溶液。聚合率係約1〇〇%。所獲得之A聚合物嵌段的 Μη係30,0〇〇 ’ PDI係丨61，聚合物組成係 MMA/BMA/LMA/MAA与加I/32,2 ’利用理論計算所計算 出的 Tg 係 7.7°C ’ 酸值係 l2.6mgKOH/g。 再者，將所採樣的溶液其中一部分添加於水中，結果會有 軟質聚合物析出。因為A聚合物嵌段係具錢基，因而具 有可溶解於鹼性水中的可能性。因此，在q m的 溶液1mL巾，添續採樣的A聚合物紐(Ug，並利用^ 攪拌器施行24小時攪拌，確認溶解性。結果，才 膠狀樹脂。由以上結果可確認到所獲得之A聚A出=色橡 未溶解於中性與鹼性的水令。 X 。物嵌段並 除了在所獲得之A聚合物嵌段的溶液中， 101108433 恭加ΜΜα Μ 30 201243008 份、MAA 13.6份、及V-7〇 0.6份的混合液之外’其餘均與 前述實施例1同樣地施行6小時聚合，形成B聚合物嵌段， 而獲得A-B嵌段共聚物的溶液。聚合率係約100%。從產率 所換算的B聚合物嵌段之組成係MMA/MAA%64/36。又， 從MAA含有量所計算出之B聚合物嵌段的酸值係 235mgKOH/g。 所獲得之A-B嵌段共聚物的Μη係35,000，PDI係1.62， 酸值係55mgKOH/g。又’從聚合產率的結果所計算出之a 聚合物嵌段與B聚合物嵌段的質量比係A/B=80.5/19.5。激 烈擾摔A-B欲段共聚物的溶液’添加28%氨水12 9份盘水 12.9份的混合液，結果獲得帶有藍色的白濁狀高黏性液體。 經添加水368.4份，結果獲得帶有藍色的低黏性白色乳液(乳 液型黏合劑(3))。經利用B型黏度計所測定的白色乳液之黏 度係56.1mPa · s，固形份濃度係24.9%。又，乳液粒子的數 量平均粒徑係132nm。 (比較例1 :水溶性聚合物） 在具備有擾掉機、回流冷凝器、溫度計、気導入管及滴液 漏斗的1L分離式燒瓶中，裝入DMDG 1〇〇份，加溫至4〇<>c。 在另-容器中裝人BzMA 35.8份、HEMA 1〇 6份、觀八43」 份、MAA 10.5份、及V-7G 3份，_拌便調製得單體混合 液。將所調製得之單體混合液的1/2量震人滴液漏斗中並施 行滴下。再歷時1.5小時滴下單體溶液剩餘的ι/2量後，於 101108433 201243008 40 C知行6小時聚合’便獲得聚合物的溶液。聚合率係約 100%。又，所獲得之聚合物的Μη係12,500，PDI係1.96， 酸值係 69.1 mgKOH/g。 激烈攪拌聚合物的溶液，添加28%氨水8.2份與水41.8 份的混合液，結果獲得具透明性的黏性液體。若添加水15〇 份’便可獲得透明的聚合物液(水溶性聚合物）。經利用B型 黏度計所測定之聚合物液的黏度係25lmPa· s，固形份濃度 係24.6。/。。所獲得之水溶性聚合物係無規共聚合體，其組成 係與實施例1所獲得之乳液型黏合劑（1)中所含有之A_B嵌 段共聚物的組成相同。 (比較例2 :乳液聚合物（1)) 除了未使用破與二苯基曱烷之外，其餘均與前述實施例2 同樣地施行第一段聚合，而獲得第一段聚合物嵌段的溶液。 聚合率係98 /〇。所獲得之第一段聚合物嵌段的Μη係 37,000，PDI係1.90。使用所獲得之第一段聚合物嵌段的溶 液，與前述實施例2同樣地施行6小時聚合，形成第二段聚 合物嵌段，而獲得嵌段聚合物的溶液。聚合率係約1〇〇%。 所獲得之嵌·段聚合物的Μη係27,000，PDI係1.95。 激烈攪拌嵌段聚合物的溶液，添加二甲基胺基乙醇17 8 份與水17.8份的混合液，結果生成白濁的白色塊狀不溶物， 攪拌困難。進一步添加水，結杲並未乳液化，獲得含有大量 析出物之不具非流動性的白色糊狀物(乳液聚合物（1))。 101108433 32In addition to 197.1 parts of DMDG, 4 parts of iodonium, 2.4 parts of V-70, 54 parts of MMA, 49 parts of butyl methacrylate (hereinafter referred to as "BMA"), and dodecyl methacrylate (hereinafter referred to as rLMA) ") A polymer was obtained in the same manner as in the above Example 1 except that 5 parts, MAA 3 parts, and a second butyl hydroxytoluene (hereinafter referred to as "ΒΗτ") 〇, 丨, and 6 hours of polymerization were carried out. Block solution. The polymerization rate is about 1%. The obtained A polymer block has a Tg system of 30,0〇〇' PDI system 61, a polymer composition system MMA/BMA/LMA/MAA and I/32, 2' calculated by theoretical calculation. The acid value of 7.7 ° C ' is l2.6 mg KOH / g. Further, a part of the sampled solution was added to water, and as a result, a soft polymer was precipitated. Since the A polymer block has a money base, it has the possibility of being soluble in alkaline water. Therefore, in a 1 mL towel of a solution of qm, a sample of A polymer (Ug) was added, and the mixture was stirred for 24 hours using a stirrer to confirm the solubility. As a result, the gel-like resin was obtained. From the above results, it was confirmed that the obtained product was obtained. A poly A out = color oak is not dissolved in neutral and alkaline water. X. Block and in addition to the solution of the obtained A polymer block, 101108433 恭α Μ 30 201243008, MAA 13.6 In the same manner as in the above Example 1, except that the mixture was mixed with V-7 〇 0.6 parts, the polymerization was carried out for 6 hours to form a B polymer block, and a solution of the AB block copolymer was obtained. 100%. The composition of the B polymer block converted from the yield is MMA/MAA% 64/36. Further, the acid value of the B polymer block calculated from the MAA content is 235 mgKOH/g. The AB block copolymer has a Μ3 system of 35,000, a PDI system of 1.62, and an acid value of 55 mgKOH/g. Further, the mass ratio of the polymer block to the B polymer block is calculated from the result of the polymerization yield. /B=80.5/19.5. The solution of the severely disturbing AB-segment copolymer 'Add 28% ammonia water 12 9 parts of water 12.9 parts mixture As a result, a white turbid highly viscous liquid with a blue color was obtained. After adding 368.4 parts of water, a low-viscosity white emulsion with blue color (emulsion type adhesive (3)) was obtained, which was measured by a B-type viscometer. The viscosity of the white emulsion was 56.1 mPa·s, and the solid concentration was 24.9%. Further, the number average particle diameter of the emulsion particles was 132 nm. (Comparative Example 1: Water-soluble polymer) In the presence of a disturbing machine, a reflux condenser In a 1 L separation flask of a thermometer, a crucible introduction tube, and a dropping funnel, 1 part of DMDG was placed and heated to 4 〇 <>c. In the other container, BzMA 35.8 parts, HEMA 1〇 were placed. 6 parts, 8:43 parts, MAA 10.5 parts, and V-7G 3 parts, _ mixes the monomer mixture. The 1/2 volume of the prepared monomer mixture is shaken in the dropping funnel. And the dropping was carried out. After the amount of the remaining ι/2 of the monomer solution was dropped for 1.5 hours, the solution of the polymer was obtained at 101108433 201243008 40 C for 6 hours. The polymerization rate was about 100%. Further, the obtained polymerization was carried out. The Μη system is 12,500, the PDI system is 1.96, and the acid value is 69.1 mgKOH/g. The solution of the polymer is stirred vigorously. Add a mixture of 8.2 parts of 28% ammonia water and 41.8 parts of water to obtain a viscous liquid with transparency. If 15 parts of water is added, a transparent polymer liquid (water-soluble polymer) can be obtained. The viscosity of the polymer solution measured by the viscometer was 25 lmPa·s, and the solid concentration was 24.6. /. . The water-soluble polymer obtained was a random copolymer having the same composition as that of the A_B block copolymer contained in the emulsion type adhesive (1) obtained in Example 1. (Comparative Example 2: Emulsion Polymer (1)) The first-stage polymerization was carried out in the same manner as in the above Example 2 except that the diphenyl-nonane was not used, and the first-stage polymer block was obtained. Solution. The polymerization rate is 98 / 〇. The obtained first polymer block had a Μ3 system of 37,000 and a PDI system of 1.90. Using the obtained solution of the first-stage polymer block, polymerization was carried out for 6 hours in the same manner as in the above Example 2 to form a second-stage polymer block, and a solution of the block polymer was obtained. The polymerization rate is about 1%. The 嵌η of the obtained inlaid segment polymer was 27,000, and the PDI system was 1.95. The solution of the block polymer was vigorously stirred, and a mixed liquid of 17 8 parts of dimethylaminoethanol and 17.8 parts of water was added, and as a result, a white turbid white insoluble matter was formed, which was difficult to stir. Further, water was added, and the crucible was not emulsified, and a non-flowable white paste (emulsion polymer (1)) containing a large amount of precipitates was obtained. 101108433 32
S 201243008 未進行乳液化的理由可認為如下。實施例1〜3中，可認為 水不溶性A聚合物嵌段會粒子化，另一方面，利用水溶性b 聚合物嵌段進行自行乳化。所以，可認為能獲得良好狀態的 乳液。相對於此，比較例2中，因為第一段聚合物嵌段與第 二段聚合物嵌段係分別獨立的不同構造聚合物，故可認為無 法利用第二段聚合物，使第一段聚合物良好地乳化。由此得 知，藉由將A-B嵌段共聚物設為特定的構造，便可依良好 狀態進行乳液化（乳化安定化）。 (比較例3 :乳液聚合物(2)) 在具備有授拌機、回流冷凝器、溫度計、氮導入管及滴液 漏斗的1L分離式燒瓶中，裝入水450份及PHOSPHANOL RD-720 (構酸酯系界面活性劑，東邦化學公司製）2.5份，加 溫至70°C。在另一容器中裝入MMA 52份、BMA 47份、 LMA 48份、及MAA 3份並進行混合，調製得單體混合液。 在分離式燒瓶内添加過硫酸鉀4份，且將所調製得之單體混 合液裝入滴液漏斗中，經添加1/4量之後，再將剩餘者歷時 1.;5小時滴下。在7〇°C進一步進行4小時熟成便獲得聚合物 溶液。所獲得之聚合物溶液係帶有藍色的白濁乳液，且在反 應系統内與授样車由觀察到若干析出物。 在所獲#之聚合物溶液中添加28%氨水2.5份，結果獲得 帶有若子透明感的白色乳液(乳液聚合物(2))。經利用B型黏 产叶測定之所獲付之白色乳液的黏度係23mPa · s ’固形份 33 101108433 201243008 濃度係25.1%。又’乳液粒子的數量平均粒徑係i〇4nm。又， 所獲得之聚合物的Μη係123,0〇〇 ’ pDI係3 63。所獲得之 聚合物的酸值係低於實施例3所獲得之A聚合物嵌段的酸 值。 (實施例4 :紅色喷墨墨水（1)之調製） 將作為紅色顏料的C.I.顏料紅-122 (二曱基啥吖酮顏料， 大曰精化工業公司製）200份、苯乙烯丙烯酸共聚合體(Μη : 5,000、酸值：215mgKOH/g)的氨中和水溶液（固形份濃度： 20%) 200份、二乙二醇單丁醚80份、及水320份，利用分 散機施行混合攪拌’調製得研磨基質。使用臥式介質分散機 「珠粒磨碎機0.6公升ECM型」（商品名，SHINMARU ENTERPRISES公司製，二氧化鍅製球珠徑：〇.5mm)，依周 速10m/s對所調製之研磨基質施行分散處理2小時，便獲得 分散液°對所獲得之分散液施行離心分離處理(7,500轉，20 分鐘)後’利用孔洞尺寸ΙΟμιη之薄膜過濾器施行過濾，添 加離子父換水，獲得顏料濃度14%的紅色顏料分散體（1)。 經使用粒度測定器「NICOMP 380ZLS-S」（International Business公司製），測定所獲得之紅色顏料分散體⑴中含有 的顏料粒子之數量平均粒徑，結果為122nm。另外’利用B 型黏度汁所測定之紅色顏料分散體（1)的黏度係3.59mPa.s。 將所择彳琦 .X件之紅色顏料分散體（1)40份、實施例1所獲得之 乳液型黏合劑（1) 24.4份、BDG 1.8份、1，2_己二醇5份、甘 101108433 34 201243008 油 10 份、「SURFYNOL#5」（商品名，AirProducts 公司製） 1份、及水17.6份進行混合’經充分攪拌後，利用孔洞尺寸 ΙΟμιη之薄膜過濾器施行過濾，獲得紅色噴墨墨水(1)。所獲 得之紅色喷墨墨水（1)的黏度係2.81mPa · s。 (比較例4 :紅色喷墨墨水(2)之調製） 除了取代乳液型黏合劑（1)，改為使用比較例1所獲得之 水溶性聚合物之外，其餘均與前述實施例4同樣地獲得紅色 喷墨墨水(2)。所獲得之紅色喷墨墨水(2)的黏度係5.69mPa · s。 依此成為高黏度的理由，可認為係因為使用水溶性聚合物所 致。 (實施例5〜7 :藍色喷墨墨水（1)、黃色喷墨墨水(1)、黑色喷 墨墨水（1)之調製） 除了取代紅色顏料(C.I.顏料紅-122)，改為使用作為藍色 顏料的C.I.顏料藍_15 : 3 (大曰精化工業公司製，花青音藍 -A220JC)、作為黃色顏料的C.L顏料黃_74(大曰精化工業公 司製 ’ SEIKAFAST YELLOW-2016G)、作為黑色顏料的 C·1. 顏料黑-7 (DEGUSSA公司製，S170)之外，其餘均與前述實 施例4同樣地獲得藍色顏料分散體（1)、黃色顏料分散體 (1)、及黑色顏料分散體（1)。所獲得之顏料分散體中含有的 顏料粒子之數量平均粒徑、及顏料分散體之黏度的測定結果 係示於表1。 101108433 35 201243008 [表i] 顏料粒子之數量平均粒徑 (nm) 黏度 (mPa · s) 紅色顏料分散體（1) 122 3.59 藍色顏料分散體（1) 121 —' 3.12 黃色顏料分散體（1) 119 2.72 黑色顏料分散體（1) 130 ' 4.21 再者’除了使用所獲得之各色顏料分散體之外，其餘均與 前述實施例4同樣地獲得藍色噴墨墨水(1)、黃色嘴墨墨水 (1)、及黑色喷墨墨水（1)。所獲得之墨水的黏度測定結果係 示於表2。 [表2] 黏度 (mPa · 實施例4 紅色喷墨墨水（1) 2JT~~~~ 實施例5 藍色喷墨墨水（1) 2^〇 實施例6 黃色喷墨墨水（1) 2^20 實施例7 黑色喷墨墨水（1) 3.2〇~~~~ 比較例4 紅色喷墨墨水(2) 5.69^~~~ 如表2所示，得知相較於比較例4所獲得之喷墨黑水，實 施例4〜7所獲得之喷墨墨水係屬低黏度。 (印刷適性評估） 將實施例4〜7及比較例4所獲得之噴墨墨水分別填充於墨 水匣中，使用Seiko Epson公司製喷墨印表機「E]V[93〇c」， 在美國Xerox公司製「Xerox紙4024」上，依高速印刷草稿 模式施行整面印刷。結果，當使用實施例4〜7所獲得之嘴墨 墨水的情況’即便印刷100張’印頭仍不會發生阻夷，列芒 物亦不會產生飛白、條紋’呈現良好列印狀態。和對於此， 101108433 36 201243008 當使用比較例4所獲得之喷墨墨水的情況，經列印7張後， 便在列印部產生條紋。然後，漸漸地條紋、飛白逐漸增加， 在第23張時便無法列印。比較例4所獲得之喷墨墨水係因 為使用水溶性聚合物’因而黏度較高，溶解的聚合物較多。 所以，可認為因非牛頓黏性導致吐出安定性降低。另一方 面，實施例4〜7所獲得之喷墨墨水可認為係因為其皮膜形成 成分（皮膜形成用黏合劑）呈粒子化，因而屬於低黏度，明顯 提升吐出安定性。 再者，經整面印刷結束後暫時停止印表機，並放置24小 時。經放置後’再度施行整面印刷。結果，使用實施例4〜7 所獲得之噴墨墨水的情況，可毫無問題地施行印刷。相對於 此，使用比較例4所獲得之喷墨墨水的情況，便無法進行印 刷。可s忍為因為貫施例4-7所獲得之噴墨墨水中含有的A-B 欣丰又共聚物’係B聚合物後段的酸值較高，且容易溶解於 水中’因而即便墨水在印頭處出現乾燥，仍可再溶解，形成 可列印狀態。另外，使用實施例2所獲得之乳液型黏合劑(2) 調製得噴墨墨水’同樣地對印刷適性進行評估，結果呈現與 實施例4〜7所獲得之喷墨墨水同樣的結果。 (實施例8 :紅色喷墨墨水(3)之調製） 在具備有攪拌機、回流冷凝器、溫度計、及氮導入管的 1L分離式燒瓶中’裝填入DMDG 295.68份、碘3.03份、 V-70 14.8份、BHT 0.66份、及曱基丙烯酸環己醋（以下記為 101108433 37 201243008 ™MA」）176.4份〜邊流通氮一邊施行攪拌，加溫至 40 C ’施行6.5小時聚合，獲得第—聚合物的溶液。對溶液 其中-部分進行採樣，娜定固形份濃度，結果為2ι ι%，產 率（不揮發份)為67%。X，_用GPC分析第—聚合物，. 結果 Μη 為 4,〇〇〇 ’ PDI 為} 37。 _ 在所獲^•之第-聚合物的溶液中，添加MMA75份MAA 25.8份、及V-70 0.45份的混合物，施行45小時的聚合， 形成第二聚合物’喊得A_B型嵌段共㈣的溶液。不揮 發份係48.3% ’確認到幾乎所有的單體均進行聚合。第二聚 合物的構造中’含有源自屬於殘留單體之CHma的構成單 位。從產率所換算的B聚合物嵌段之組成係 MMA/MAA/CHMA=59/2〇/2b所獲得之嵌段共聚物的Mn 係 6,200 ’ PDI 係 1.41 ’ 酸值係 6i.3mgKOH/g。 在嵌段共聚物的溶液中添加BDG 147 8份。進一步添加 氫氧化鈉18.5份與水129.3份的混合液而進行中和，結果獲 得透明的液體(嵌段共聚物型顏料分散劑）。另外，完全沒有 析出物’固形份濃度係34.4%。 · 將上述嵌段共聚物型顏料分散劑143份、BDG 8〇份及 . 純水377 f”進行混合’獲得相且沒有析出物與混濁的均勻 溶液。在所獲得之溶液中，添加作為紅色顏料的C丄顏料紅 122(一曱基嗜。丫嗣顏料’大日精化工業公司製）細份利 用分散機解凝而調製得研磨基1使祕式介質分散機「珠 101108433 201243008 边十機0.6公升ECM型」（商品名， enterprises公司製，二氧化錯製球珠徑：〇 5随），依周 速l〇m/S對所調製得之研磨基質施行分散處理2小時，便獲 得分散液。對所獲得之分散請份，依顏料丨農度成為14二 的方式添加離子交換水3，綱份。—邊_ —邊滴下抓醋 酸。另外，初期的pH係、9.5，藉由滴下5%醋酸而下降至 pH4.5 ’便獲得水性顏料分散液。經過遽所獲得之水性顏料 分散液後，利用離子交換水充分洗淨，便獲得經顏料分散劑 所被覆的顏料糊（固形份濃度：3〇.5〇/。）。 在上述顏料糊700份中，添加使BDG 94份與氫氧化納 1.15份溶解於水29讀中而得的溶液。施行授摔而解凝後， 使用前述臥式介質分散機施行分散處理。接著，使用超高壓 均質機「微射流均質機」（Microfluidics公司製），依15〇MPa 且3通道施行分散處理而獲得分散液。所獲得之分散液經施 行離心分離處理(7,500轉、20分鐘)後，利用孔洞尺寸1〇μιη 之薄膜過濾、器施彳亍過遽，添加離子交換水，便獲得顏料濃度 14%的紅色顏料分散體(2)。經使用粒度測定器「NIC〇Mp 380ZLS-S」（International Business 公司製），測定所獲得之 紅色顏料分散體(2)中含有的顏料粒子的數量平均粒徑，結 果為108nm。另外，經利用B型黏度計所測定之紅色顏料 分散體(2)的黏度係2.22mPa · s。將該紅色顏料分散體(2)於 7〇°C保存一週，結果顏料的粒徑與黏度並無變化，保存安定 101108433 39 201243008 性呈良好。 將所獲得之紅色顏料分散體(2) 40份、實施例3所獲得之 乳液型黏合劑（3) 24.4份、BDG 1.8份、1,2-己二醇5份、甘 油 10 份、「SURFYNOL 465」（商品名，Air Products 公司製） 1份、及水35.6份進行混合，經充分攪拌後，利用孔洞尺寸 1 Ομιη之薄膜過濾器施行過濾，獲得紅色喷墨墨水(3)。所獲 得之紅色喷墨墨水(3)的黏度係3.OmPa · s。又，紅色喷墨.墨 水(3)中所含有之顏料粒子的數量平均粒徑係l〇8nm。 (實施例9〜11 :藍色喷墨墨水(2)、黃色喷墨墨水(2)、黑色嘴 墨墨水(2)之調製） 除了取代紅色顏料(C.I.顏料紅-122)，改為使用作為藍色 顏料的C.I·顏料藍-15 : 3 (大曰精化工業公司製，花青芽藍 -A220JC)、作為黃色顏料的C.I.顏料黃-74 (大曰精化工業公 司製，SEIKAFAST YELLOW-2016G)、作為黑色顏料的αι 顏料黑-7(DEGUSSA公司製，Sl7〇)之外，其餘均與前述實 施例8同樣地獲得藍色顏料分散體(2)、黃色顏料分散體 (2)、及黑色顏料分散體(2)。所獲得之顏料分散體中含有的 顏料粒子的數量平均粒徑、及顏料分散體的黏度之測定、结i 係示於表3。 101108433 40 201243008 [表3] 紅色顏料分散體（2) (nm) 黏度 (mPa · s) ϋ顏料分散體(2)S 201243008 The reason why no emulsion is not formed is considered as follows. In Examples 1 to 3, it is considered that the water-insoluble A polymer block is pelletized, and on the other hand, the water-soluble b polymer block is self-emulsified. Therefore, it can be considered that an emulsion in a good state can be obtained. On the other hand, in Comparative Example 2, since the first-stage polymer block and the second-stage polymer block are respectively different from each other, it is considered that the second-stage polymer cannot be used to make the first-stage polymerization. The material is well emulsified. From this, it is understood that by setting the A-B block copolymer to a specific structure, it is possible to carry out emulsion formation (emulsification stabilization) in a good state. (Comparative Example 3: Emulsion Polymer (2)) In a 1 L separation flask equipped with a mixer, a reflux condenser, a thermometer, a nitrogen introduction tube, and a dropping funnel, 450 parts of water and PHOSPHANOL RD-720 ( The acid ester-based surfactant (manufactured by Toho Chemical Co., Ltd.) was added in an amount of 2.5 parts and heated to 70 °C. In a separate container, 52 parts of MMA, 47 parts of BMA, 48 parts of LMA, and 3 parts of MAA were placed and mixed to prepare a monomer mixture. To the separable flask, 4 parts of potassium persulfate was added, and the prepared monomer mixture was placed in a dropping funnel, and after adding 1/4 amount, the remaining one was dripped for 1.5 hours. The polymer solution was obtained by further aging at 7 ° C for 4 hours. The polymer solution obtained was provided with a blue, white turbid emulsion, and several precipitates were observed in the reaction system from the sample car. To the polymer solution obtained #, 2 parts of 28% aqueous ammonia was added, and as a result, a white emulsion (emulsion polymer (2)) having a transparent color was obtained. The viscosity of the white emulsion obtained by the B-type cohesive leaf was 23 mPa · s 'solids 33 101108433 201243008 Concentration 25.1%. Further, the number average particle diameter of the emulsion particles is i 〇 4 nm. Further, the obtained polymer had a Μη123,0〇〇' pDI system of 3 63. The acid value of the obtained polymer was lower than that of the A polymer block obtained in Example 3. (Example 4: Preparation of Red Inkjet Ink (1)) 200 parts of CI Pigment Red-122 (dioxinone pigment, manufactured by Otsuka Seika Chemical Co., Ltd.) as a red pigment, styrene acrylic copolymer (Μη : 5,000, acid value: 215 mgKOH/g), an aqueous solution of ammonia neutralization (solid content: 20%), 200 parts, 80 parts of diethylene glycol monobutyl ether, and 320 parts of water, and mixed by a disperser. The substrate is prepared to be ground. Using a horizontal medium disperser "bead mill 0.6 liter ECM type" (trade name, manufactured by SHINMARU ENTERPRISES, ruthenium dioxide ball diameter: 〇.5 mm), the prepared grinding is performed at a peripheral speed of 10 m/s. The substrate was subjected to dispersion treatment for 2 hours to obtain a dispersion. The obtained dispersion was subjected to centrifugal separation treatment (7,500 rpm, 20 minutes), and then filtered using a membrane filter having a pore size of ιμηη, and an ion parent was added to change water to obtain a pigment concentration. 14% red pigment dispersion (1). The number average particle diameter of the pigment particles contained in the obtained red pigment dispersion (1) was measured by a particle size measuring device "NICOMP 380ZLS-S" (manufactured by International Business Co., Ltd.) and found to be 122 nm. Further, the viscosity of the red pigment dispersion (1) measured by the B-type viscosity juice was 3.59 mPa·s. 40 parts of the red pigment dispersion (1) of the selected Qiqi.X piece, 24.4 parts of the emulsion type adhesive (1) obtained in Example 1, 1.8 parts of BDG, 5 parts of 1,2-hexanediol, and 101108433 34 201243008 10 parts of oil, "SURFYNOL #5" (trade name, manufactured by AirProducts) 1 part, and 17.6 parts of water were mixed. After thorough stirring, the membrane filter was used to filter the pore size ΙΟμηη to obtain red inkjet. Ink (1). The obtained red inkjet ink (1) had a viscosity of 2.81 mPa·s. (Comparative Example 4: Preparation of Red Inkjet Ink (2)) The same procedure as in the above Example 4 was carried out, except that the emulsion type adhesive (1) was used instead of the water-soluble polymer obtained in Comparative Example 1. Obtained red inkjet ink (2). The viscosity of the obtained red inkjet ink (2) was 5.69 mPa·s. The reason for this is a high viscosity, which is considered to be due to the use of a water-soluble polymer. (Examples 5 to 7: Preparation of blue inkjet ink (1), yellow inkjet ink (1), and black inkjet ink (1)) In place of the red pigment (CI Pigment Red-122), it was used instead. CI pigment blue of blue pigment _15 : 3 (made by Otsuka Seika Co., Ltd., Huaqing blue - A220JC), CL pigment yellow as yellow pigment _74 (made by Otsuka Seika Co., Ltd.) SEIKAFAST YELLOW-2016G A blue pigment dispersion (1) and a yellow pigment dispersion (1) were obtained in the same manner as in Example 4 except that C.1. Pigment Black-7 (manufactured by DEGUSSA Co., Ltd., S170) was used as the black pigment. And black pigment dispersion (1). The measurement results of the number average particle diameter of the pigment particles contained in the obtained pigment dispersion and the viscosity of the pigment dispersion are shown in Table 1. 101108433 35 201243008 [Table i] Number average particle size (nm) of pigment particles Viscosity (mPa · s) Red pigment dispersion (1) 122 3.59 Blue pigment dispersion (1) 121 — ' 3.12 Yellow pigment dispersion (1 119 2.72 Black Pigment Dispersion (1) 130 ' 4.21 Further, blue inkjet ink (1) and yellow ink were obtained in the same manner as in Example 4 except that the obtained pigment dispersions were used. Ink (1), and black inkjet ink (1). The viscosity measurement results of the obtained inks are shown in Table 2. [Table 2] Viscosity (mPa · Example 4 Red inkjet ink (1) 2JT~~~~ Example 5 Blue inkjet ink (1) 2^〇Example 6 Yellow inkjet ink (1) 2^20 Example 7 Black inkjet ink (1) 3.2〇~~~~ Comparative Example 4 Red inkjet ink (2) 5.69^~~~ As shown in Table 2, the inkjet obtained in Comparative Example 4 was obtained. In the black water, the inkjet inks obtained in Examples 4 to 7 were low in viscosity. (Printability evaluation) The inkjet inks obtained in Examples 4 to 7 and Comparative Example 4 were respectively filled in an ink cartridge, using Seiko Epson. The company's inkjet printer "E]V[93〇c" was printed on the Xerox paper 4024 made by Xerox, USA, and printed on the high-speed printing draft mode. As a result, it was obtained using Examples 4 to 7. In the case of ink in the mouth, even if 100 prints are printed, the print head will not be blocked, and the white matter will not produce white and stripes, which will give a good print status. And for this, 101108433 36 201243008 when using Comparative Example 4 In the case of the obtained inkjet ink, after printing 7 sheets, streaks are generated in the printing portion. Then, gradually striping and flying Increasingly, it could not be printed on the 23rd sheet. The inkjet ink obtained in Comparative Example 4 is based on the use of a water-soluble polymer, so the viscosity is higher and there are more dissolved polymers. Therefore, it can be considered that it is non-Newtonian. On the other hand, the inkjet inks obtained in Examples 4 to 7 are considered to be low in viscosity because of the film formation component (adhesive for forming a film), and the discharge is stable. Furthermore, after the whole surface printing is finished, the printer is temporarily stopped and placed for 24 hours. After being placed, the whole surface printing is performed again. As a result, the inkjet inks obtained in Examples 4 to 7 can be used. Printing was carried out without any problem. On the other hand, in the case of using the inkjet ink obtained in Comparative Example 4, printing could not be performed. It can be tolerated because of the AB contained in the inkjet ink obtained in Example 4-7. Xinfeng and Copolymer 'B-polymers have higher acid value and easy to dissolve in water'. Therefore, even if the ink is dry at the printing head, it can be redissolved to form a printable state. The emulsion type adhesive (2) obtained in Example 2 was prepared to evaluate the printability of the inkjet ink. The results were the same as those of the inkjet inks obtained in Examples 4 to 7. (Example 8: Red Preparation of inkjet ink (3) In a 1 L separation flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube, 295.68 parts of DMDG, 3.03 parts of iodine, 14.8 parts of V-70, and BHT 0.66 were charged. 176.4 parts of the hexyl hexanoic acid sulfonic acid (hereinafter referred to as 101108433 37 201243008 TMMA) was stirred while flowing nitrogen, and heated to 40 C' for 6.5 hours to obtain a solution of the first polymer. The - part of the solution was sampled, and the concentration of the solid was determined to be 2% by weight, and the yield (nonvolatile content) was 67%. X, _ was analyzed by GPC for the first polymer, and the result was Μη 4 and 〇〇〇 'PDI was 37. _ Adding a mixture of MMA 75 parts of MAA 25.8 parts and V-70 0.45 parts in a solution of the obtained first polymer, performing 45 hours of polymerization to form a second polymer 'cry A_B type block (d) solution. 48.3% of the non-volatile fraction was confirmed to confirm that almost all of the monomers were polymerized. The structure of the second polymer ' contains constituent units derived from CHma belonging to the residual monomer. The Mn system of the block copolymer obtained from the composition of the B polymer block converted from the yield of MMA/MAA/CHMA=59/2〇/2b is 6,200 'PDI system 1.41 'acid value 6i.3 mgKOH/g . 8 parts of BDG 147 were added to the solution of the block copolymer. Further, a mixture of 18.5 parts of sodium hydroxide and 129.3 parts of water was added to carry out neutralization, and as a result, a transparent liquid (block copolymer type pigment dispersant) was obtained. Further, there was no precipitate at all, and the solid concentration was 34.4%. · 143 parts of the above block copolymer type pigment dispersant, BDG 8 parts and pure water 377 f" were mixed to obtain a homogeneous solution with no precipitate and turbidity. In the obtained solution, added as red The C 丄 pigment red 122 of the pigment (manufactured by Daiichi Seiki Co., Ltd.) was finely dispersed by a disperser to prepare a polishing base 1 to make a secret medium disperser "bead 101108433 201243008 side ten machine 0.6 liter ECM type" (trade name, manufactured by the company, oxidized wrong ball diameter: 〇5), and the prepared grinding substrate was dispersed for 2 hours at a peripheral speed of l〇m/S to obtain dispersion. liquid. Ion-exchanged water 3 is added to the obtained dispersion amount in such a manner that the pigment agronomy is 14 two. - Edge _ - dripping vinegar acid. Further, the initial pH system and 9.5 were reduced to pH 4.5 by dropping 5% acetic acid to obtain an aqueous pigment dispersion. After the aqueous pigment dispersion obtained by hydrazine was sufficiently washed with ion-exchanged water, a pigment paste (solid content concentration: 3 〇.5 〇/.) which was coated with the pigment dispersant was obtained. To 700 parts of the above pigment paste, a solution obtained by dissolving 94 parts of BDG and 1.15 parts of sodium hydroxide in water 29 was added. After de-coagulation by the application of the drop, the dispersion treatment was carried out using the above-described horizontal medium disperser. Then, using a super-high pressure homogenizer "micro-jet homogenizer" (manufactured by Microfluidics Co., Ltd.), a dispersion liquid was obtained by performing dispersion treatment at 15 MPa and three channels. The obtained dispersion was subjected to centrifugal separation treatment (7,500 rpm, 20 minutes), and then subjected to membrane filtration using a pore size of 1 〇 μηη, and then ion-exchanged water was added to obtain a red pigment having a pigment concentration of 14%. Dispersion (2). The number average particle diameter of the pigment particles contained in the obtained red pigment dispersion (2) was measured by using a particle size measuring device "NIC〇Mp 380ZLS-S" (manufactured by International Business Co., Ltd.), and the result was 108 nm. Further, the viscosity of the red pigment dispersion (2) measured by a B-type viscometer was 2.22 mPa·s. The red pigment dispersion (2) was stored at 7 ° C for one week, and as a result, the particle size and viscosity of the pigment did not change, and the retention stability was good in the stability of 101108433 39 201243008. 40 parts of the obtained red pigment dispersion (2), 24.4 parts of the emulsion type adhesive (3) obtained in Example 3, 1.8 parts of BDG, 5 parts of 1,2-hexanediol, 10 parts of glycerin, "SURFYNOL" 465" (trade name, manufactured by Air Products Co., Ltd.) and 1 part of water and 35.6 parts of water were mixed, and after sufficiently stirring, filtration was carried out using a membrane filter having a pore size of 1 Ομηη to obtain a red inkjet ink (3). The viscosity of the obtained red inkjet ink (3) was 3.OmPa · s. Further, the number average particle diameter of the pigment particles contained in the red inkjet ink (3) is 10 nm 8 nm. (Examples 9 to 11: Preparation of blue inkjet ink (2), yellow inkjet ink (2), black inkjet ink (2)) In addition to replacing the red pigment (CI Pigment Red-122), it was used instead. CI pigment blue-15 of blue pigment: 3 (made by Otsuka Seika Co., Ltd., flower blue bud blue-A220JC), CI pigment yellow-74 as yellow pigment (made by Otsuka Seika Co., Ltd., SEIKAFAST YELLOW- In the same manner as in the above-mentioned Example 8, the blue pigment dispersion (2) and the yellow pigment dispersion (2) were obtained in the same manner as in the above Example 8 except that the α1 pigment black-7 (manufactured by DEGUSSA Co., Ltd., Sl7〇) was used as the black pigment. And black pigment dispersion (2). The measurement of the number average particle diameter of the pigment particles contained in the obtained pigment dispersion and the viscosity of the pigment dispersion is shown in Table 3. 101108433 40 201243008 [Table 3] Red pigment dispersion (2) (nm) Viscosity (mPa · s) ϋ pigment dispersion (2)
再者除了使用所獲得之各色顏料分散體，調整 水量，並將黏度全部設成3.5mPa · s之外，其料“= 施例8同樣地獲得藍色喷墨墨水(2)、黃色噴墨墨水 黑色喷墨墨水(2)。所獲得之墨水中含有的顏料粒、， 平均粒徑、及墨水的黏度之測定結果係示於表4。 量 (比較例5 :紅色噴墨墨水(4)之調製） 除了取代乳液型黏合劑(3) ’改為使用比較例3所獲得 乳液聚合物(2)之外，其餘均與前述實施例8同樣地獲：: 色喷墨墨水(4)。所獲得之墨水巾含有的顏料粒子的 均粒徑、及墨水的黏度之測定結果係示於表4。 ” [表4] 實施例8 實施例9 顏料粒子之徑 (nm) "s~s (mPa · 紅色士墨墨水m 奸 4» 上----- 115 ------1- 3.5 藍色噴墨專7以2、 91 3l~~~ il~ 3l f施例10 黃色喷墨1皮ru 124 f施例11 比較例5 ，黑色噴墨畧 紅色喷墨墨水(4) 108 3.5 使用嵌J又共聚物型顏料分散劑的情況，顏料分散體、與使 用其之喷墨墨水均屬低黏度化。又，關於使用含有界面活性 劑之乳液聚合物(2)的紅色喷墨墨水(4)，亦能夠低黏度化。 101108433 41 201243008 此結果可認為係任一 致。 情況均添加經粒子化的低黏度乳液所 依照與前述「印刷適性^ 忒驗」同樣的順序，使用實施例 8〜11與比較例5所獲得 之噴墨墨水施行高速印刷（整面印 刷）〇結果，不管使用何種喑 裡喂墨墨水的情況，均呈良好的列 印狀態。又，依照與前述r印说卜态从 ^即刷適性試驗」同樣的順序，在 整面印刷結束後暫時停止印表機，經放置24小時後，再度 施行整面印刷。結果，使用實施例8〜u所獲得之喷墨墨水 的情況’可毫無問題地施行印刷。相對於此，使用比較例5 所獲得之喷墨墨水的情況，便無法進行印刷》可認為由於在 調製比較例5的紅色喷墨墨水(4)時所添加之乳液聚合物 (2)，若在印頭處出現乾燥’便會形成膜狀態且無法呈再溶 解性的緣故。相對於此，在調製實施例8〜11的喷墨墨水時 所添加的乳液型黏合劑（3) ’係含有具高酸值之b聚合物嵌 段的水溶性A-B嵌段共聚物。所以，可認為即便墨水在印 頭處出現乾燥，當再度施行印刷時便可迅速溶解。 再者，使用實施例8〜11所獲得之喷墨墨水，對基材(PET 薄膜及氣乙烯薄片）施行印刷。經印刷後，將基材放入70°C 乾燥機中5分鐘而予以乾燥。在基材的印刷面貼上赛珞玢 帶’施行一口氣撕開的賽珞玢帶剝離試驗(JIS_K5600)之類似 試驗，結果不管使用何種喷墨墨水的情況，列印物均沒有剝 離。又，即便用指甲刮抓列印物，列印物仍不會剝離，得知 101108433 42 201243008 均具有良好的膜物性。由以上得知，使用本發明的乳液型黏 合劑所獲得之喷墨墨水，可形成對基材呈良好密接性的皮 膜。又，對列印物施行在70°C水浴恆溫槽浸潰1小時後， 觀察是否發生膨脹、白化、及龜裂等的耐水性試驗。結果， 在試驗前後幾乎沒有出現變化。又，即便施行上述賽珞玢帶 剝離試驗，列印物仍不會剝離。 (產業上之可利用性） 若使用本發明的乳液型黏合劑，可提供特別能因應高速印 刷的喷墨用水性顏料墨水。 101108433 43Further, in addition to using the obtained color pigment dispersions, the amount of water was adjusted, and the viscosity was set to 3.5 mPa·s, the material "= Example 8 similarly obtained blue inkjet ink (2), yellow inkjet Ink black inkjet ink (2). The measurement results of the pigment particles, the average particle diameter, and the viscosity of the ink contained in the obtained ink are shown in Table 4. (Comparative Example 5: Red inkjet ink (4) The preparation was carried out in the same manner as in the above Example 8 except that the emulsion type adhesive (3) was replaced with the emulsion polymer (2) obtained in Comparative Example 3: Color inkjet ink (4). The measurement results of the average particle diameter of the pigment particles contained in the obtained ink towel and the viscosity of the ink are shown in Table 4. [Table 4] Example 8 Example 9 Pigment particle diameter (nm) "s~s (mPa · Red ink ink m rape 4» On----- 115 ------1- 3.5 Blue inkjet 7 to 2, 91 3l~~~ il~ 3l f Example 10 Yellow spray Ink 1 ru 124 f Example 11 Comparative Example 5, Black Inkjet Crimson Inkjet Ink (4) 108 3.5 In the case of using a J-copolymer type pigment dispersant, a pigment dispersion, and The inkjet inks used therein are all low-viscosity. Moreover, the red inkjet ink (4) using the emulsion polymer (2) containing a surfactant can also be made low-viscosity. 101108433 41 201243008 This result can be considered as In all cases, the particle-coated low-viscosity emulsion was added in the same order as the above-mentioned "printing suitability test", and the inkjet inks obtained in Examples 8 to 11 and Comparative Example 5 were used for high-speed printing (full surface). Printing) As a result, regardless of the type of ink used to feed the ink, it is in a good printing state. In addition, it is printed on the entire surface in the same order as the above-mentioned r-printing method. After the completion of the printing, the printer was temporarily stopped, and after 24 hours of storage, the entire surface printing was again performed. As a result, the printing ink of the inkjet inks obtained in Examples 8 to u was used to perform printing without any problem. In the case of the inkjet ink obtained in Comparative Example 5, printing could not be performed". It can be considered that the emulsion polymer (2) added when the red inkjet ink (4) of Comparative Example 5 was prepared was present at the printing head. In contrast, the emulsion type adhesive (3) added in the preparation of the inkjet inks of Examples 8 to 11 contains a high acid value. b. A water-soluble AB block copolymer of a polymer block. Therefore, even if the ink is dried at the print head, it can be quickly dissolved when printing is again performed. Further, the sprays obtained in Examples 8 to 11 are used. The ink was applied to the substrate (PET film and vinyl sheet), and after printing, the substrate was dried in a 70 ° C dryer for 5 minutes. A similar test of the celluloid tape peeling test (JIS_K5600) was carried out on the printing surface of the substrate, and the printed matter was not peeled off regardless of the ink jet ink used. Moreover, even if the printed matter is scratched with a nail, the printed matter does not peel off, and it is known that 101108433 42 201243008 has good film properties. From the above, it is known that the inkjet ink obtained by using the emulsion type adhesive of the present invention can form a film having good adhesion to a substrate. Further, the printed matter was subjected to a water bath test at 70 ° C for 1 hour, and it was observed whether or not a water resistance test such as swelling, whitening, and cracking occurred. As a result, there was almost no change before and after the test. Further, even if the above celluloid strip peeling test is carried out, the printed matter does not peel off. (Industrial Applicability) When the emulsion type adhesive of the present invention is used, an aqueous inkjet ink for inkjet which is particularly capable of printing at a high speed can be provided. 101108433 43